EP1537249A2 - Age-hardening copper-base alloy and processing - Google Patents

Age-hardening copper-base alloy and processing

Info

Publication number
EP1537249A2
EP1537249A2 EP03754452A EP03754452A EP1537249A2 EP 1537249 A2 EP1537249 A2 EP 1537249A2 EP 03754452 A EP03754452 A EP 03754452A EP 03754452 A EP03754452 A EP 03754452A EP 1537249 A2 EP1537249 A2 EP 1537249A2
Authority
EP
European Patent Office
Prior art keywords
alloy
copper
reduction
electrical conductivity
yield strength
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP03754452A
Other languages
German (de)
French (fr)
Other versions
EP1537249A4 (en
EP1537249B1 (en
Inventor
Ronald N. Caron
Peter W. Robinson
Derek E. Tyler
Andreas Boegel
Hans-Achim Kuhn
Joerg Seeger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wieland Werke AG
GBC Metals LLC
Original Assignee
Wieland Werke AG
Olin Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wieland Werke AG, Olin Corp filed Critical Wieland Werke AG
Publication of EP1537249A2 publication Critical patent/EP1537249A2/en
Publication of EP1537249A4 publication Critical patent/EP1537249A4/en
Application granted granted Critical
Publication of EP1537249B1 publication Critical patent/EP1537249B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—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
    • 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

  • This invention relates to an age-hardening copper-base alloy and a processing method to make commercially useful products from that alloy. More particularly, a copper alloy containing from 0.35% to 5%, by weight, titanium is wrought to finish gauge by a process that includes an in-process solution anneal and at least one age anneal. The resultant product has an electrical conductivity in excess of 50% IACS and a yield strength in excess of 724 MPa (105 ksi). Throughout this patent application, all compositions are in weight percent and all mechanical and electrical testing was performed at room temperature (nominally 22°C), unless otherwise specified. The word “about” implies ⁇ 10% and the word "base” as in copper-base, means the alloy contains at least 50%, by weight, of the specified base element. The terms “rolling” or “rolled” are intended to encompass drawing or drawn or any other form of cold reduction, for example, as used in the manufacture and processing of wire, rod or tubing.
  • electrical connectors are formed from copper-base alloys. Properties important for an electrical connector include yield strength, bend formability, resistance to stress relaxation, modulus of elasticity, ultimate tensile strength and electrical conductivity.
  • Target values for these properties and the relative importance of the properties are dependent on the intended application of products manufactured from the subject copper alloys.
  • the following property descriptions are generic for many intended applications, but the target values are specific for under the hood automotive applications.
  • the yield strength is the stress at which a material exhibits a specified deviation, typically an offset of 0.2%, from proportionality of stress and strain. This is indicative of the stress at which plastic deformation becomes dominant with respect to elastic deformation. It is desirable for copper alloys utilized as connectors to have a yield strength of at least 724 MPa. Stress relaxation becomes apparent when an external stress is applied to a metallic strip in service, such as when the strip is loaded after having been bent into a connector. The metal reacts by developing an equal and opposite internal stress. If the metal is held in a strained position, the internal stress will decrease as a function of both time and temperature. This phenomenon occurs because of the conversion of elastic strain in the metal to plastic, or permanent strain, by microplastic flow.
  • Copper based electrical connectors must maintain above a threshold contact force on a mating member for prolonged times for good electrical connection. Stress relaxation reduces the contact force to below the threshold leading to an open circuit. It is desirable for a copper alloy for connector applications to maintain at least 95% of the initial stress when exposed to a temperature of 105°C for 1000 hours and to maintain at least 85% of the initial stress when exposed to a temperature of 150°C for 1000 hours.
  • the modulus of elasticity also known as Young's modulus, is a measure of the rigidity or stiffness of a metal and is the ratio of stress to corresponding strain in the elastic region.
  • MBR minimum bend radius
  • Bend formability may be expressed as, MBR/t, where t is the thickness of the metal strip.
  • MBR/t is a ratio of the minimum radius of curvature of a mandrel about which the metallic strip can be bent without failure to the thickness of the strip.
  • the "mandrel" test is specified in ASTM (American Society for Testing and Materials) designation E290-92, entitled Standard Test Method for Semi-Guided Bend Test for Ductility of Metallic Materials.
  • the MBR/t prefferably be substantially isotropic, a similar value in the "good way”, bend axis perpendicular to the rolling direction of the metallic strip, as well as the “bad way”, bend axis parallel to the rolling direction of the metallic strip. It is desirable for the MBR/t to be about 1.5 or less for a 90° bend and about 2 or less for a 180° bend.
  • the bend formability for a 90° bend may be evaluated utilizing a block having a V-shaped recess and a punch with a working surface having a desired radius.
  • V-block a strip of the copper alloy in the temper to be tested is disposed between the block and the punch and when the punch is driven down into the recess, the desired bend is formed in the strip.
  • V-block method related to the V-block method is the 180° "form punch” method in which a punch with a cylindrical working surface is used to shape a strip of copper alloy into a 180° bend.
  • both methods give quantifiable bendability results and either method may be utilized to determine relative bendability.
  • the ultimate tensile strength is a ratio of the maximum load a strip withstands before failure during a tensile test divided by the initial cross-sectional area of the strip. It is desirable for the ultimate tensile strength to be approximately 760 MPa. Electrical conductivity is expressed in % IACS (International Annealed
  • Copper-base alloys containing titanium are disclosed in United States patent numbers 4,601 ,879 and 4,612,167, among others.
  • the 4,601 ,879 patent discloses a copper-base alloy containing 0.25% to 3.0% of nickel, 0.25% to 3.0% of tin and 0.12% to 1.5% of titanium.
  • Exemplary alloys have an electrical conductivity of between 48.5% and 51.4% IACS and a yield strength of between 568.8 MPa and 579.2 MPa (82.5 ksi and 84 ksi).
  • the 4,612,167 patent discloses a copper alloy containing 0.8% to 4.0% of nickel and 0.2% to 4.0% of titanium. Exemplary alloys have an electrical conductivity of 51% IACS and a yield strength of 663.3 MPa and 679.2 MPa (96.2 ksi to 98.5 ksi).
  • AMAX Copper, Inc. (Greenwich, CT) has commercialized copper-nickel- titanium alloys having nominal compositions of Cu-2%Ni-1 %Ti and Cu-5%Ni- 2.5%Ti.
  • the reported properties for the Cu-2%Ni-1 %Ti alloy are yield strength 441.3 MPa-551.6 MPa (64 - 80 ksi); ultimate tensile strength 503.3 MPa-655.0 MPa (73 - 95 ksi); elongation 9%; and electrical conductivity 50 - 60% IACS.
  • the reported properties for the Cu-5%Ni-2.5%Ti alloy are yield strength 620.6 MPa- 689.5MPa (90 - 100 ksi); ultimate tensile strength 744.7 MPa (108 ksi) UTS; elongation 10 %; and electrical conductivity 40 - 53% IACS.
  • an age-hardening copper-base alloy and methods to process this alloy to form a commercially useful product for any application requiring high yield strength and moderately high electrical conductivity.
  • Typical forms for the product include strip, plate, wire, foil, tube, powder or cast form.
  • the alloys when processed according to the methods of the invention achieve a yield strength of at least 724 MPa (105 ksi) and an electrical conductivity of 50% IACS making the alloys particularly suited for use in electrical connectors and interconnections.
  • the alloys consisting essentially of, by weight, from 0.35% to 5% titanium, from 0.001% to 10% of X, where X is selected from Ni, Fe, Sn, P, Al, Zn, Si, Pb, Be, Mn, Mg, Bi, S, Te, Se, Ag, As, Sb, Zr, B, Cr and Co and combinations thereof and the balance is copper and inevitable impurities.
  • the alloy has an electrical conductivity of at least 50% IACS and a yield strength of at least 105 ksi..
  • the alloy consists essentially of from 0.35% to 2.5% titanium, from 0.5% to 5.0% nickel, from 0.5% to 0.8% of iron, cobalt and mixtures thereof, from 0.01 % to 1.0% magnesium, up to 1 % of Cr, Zr, Ag and combinations thereof and the balance is copper and inevitable impurities.
  • Figure 1 illustrates in flow chart format a first method for processing the copper alloys of the invention.
  • Figure 2 illustrates in flow chart format a second method for processing the copper alloys of the invention.
  • Figure 3 illustrates in flow chart format a third method for processing the copper alloys of the invention.
  • Copper alloys having a combination of strength and electrical conductivity, as well as good formability and a resistance to stress relaxation are in demand for many electrical current carrying applications.
  • Two exemplary applications are under-the-hood automotive applications and multimedia applications (such as computers, DVD players, CD readers and the like).
  • the alloy compositions when processed by the methods of this invention surprisingly provide an optimum combination of properties for meeting the needs for both automotive and multimedia applications, as well as other electrical and electronic applications.
  • the alloys can provide moderately high strength along with high conductivity and moderately high conductivity along with very high strength.
  • the alloys of the present invention have compositions containing Cu-Ti-X, where X is selected from Ni, Fe, Sn, P, Al, Zn, Si, Pb, Bi, S, Te, Se, Be, Mn, Mg, Ag, As, Sb, Zr, B, Cr and Co and combinations thereof.
  • X is selected from Ni, Fe, Sn, P, Al, Zn, Si, Pb, Bi, S, Te, Se, Be, Mn, Mg, Ag, As, Sb, Zr, B, Cr and Co and combinations thereof.
  • the titanium content is from 0.35% to 5% and the sum total of the "X" elements is from 0.001 % to 10%.
  • Oxygen, sulfur and carbon may be present in the alloys of the invention in amounts typically found in either electrolytic (cathode) copper or remelted copper or copper alloy scrap. Typically, the amount of each of these elements will be in the range of from about 2 ppm to about 50 ppm and preferably, each is present in an amount of less than 20 ppm. Other additions that influence the properties of the alloy may also be included. Such additions include those that improve the free machinability of the alloy, such as bismuth, lead, tellurium, sulfur and selenium. When added to enhance free machinability, these additions may be present in an amount of up to 2%. Preferably, the total of free machinability additions is between about 0.8% and 1.5%.
  • Typical impurities found in copper alloys, particularly in copper alloys formed from recycled or scrap copper may be present in an amount of up to about 1%, in total.
  • such impurities include magnesium, aluminum, silver, silicon, cadmium, bismuth, manganese, cobalt, germanium, arsenic, gold, platinum, palladium, hafnium, zirconium, indium, antimony, chromium, vanadium, and beryllium.
  • Each impurity should be present in an amount of less than 0.35%, and preferably in an amount of less than 0.1%.
  • the titanium content is from 0.35% to 2.5% and in a most preferred embodiment, the titanium content is from 0.8% to 1.4%
  • X should preferably be effective to cause titanium to precipitate from solution during an age anneal.
  • Suitable elements for "X" to enhance such precipitation include Ni, Fe, Sn, P, Al, Si, S, Mg, Cr, Co and combinations of these elements.
  • Ni One preferred addition is nickel.
  • a combination of Ni and Ti provides precipitates of CuNiTi and the presence of Fe and Ti provides precipitates of Fe 2 Ti.
  • Mg increases stress relaxation resistance and softening resistance in finished gauge and temper products.
  • the Mg also provides softening resistance during in-process aging annealing heat treatments.
  • additions of Cr, Zr and/or Ag provide increased strengthening without unduly reducing conductivity.
  • One preferred alloy in accordance with the invention that has an improved combination of yield strength, electrical conductivity, stress relaxation resistance, along with modest levels of bendability consists essentially of about 0.5 - 5.0% Nickel about 0.35 - 2.5% Titanium about 0.5 - 0.8% Iron or Cobalt about 0.01 - 1.0% Magnesium, with optionally up to about 1.0% of one or more of Sn, P, Al, Zn, Si, Pb, Bi, S, Te, Se, Be, Mn, Mg, Ag, As, Sb, Zr, B, Cr and mixtures thereof, and the balance copper and impurities.
  • the optional elements comprise up to 1% of one or more of Cr, Zr and Ag.
  • the alloy composition and processing provide a yield strength of at least about 793 MPa (115 ksi) and preferably a yield strength of at least about 827 MPa (120 ksi).
  • the conductivity is up to about 40% IACS.
  • the composition and processing provide a yield strength of more than about 724 MPa (105 ksi), and preferably up to about 793 MPa (115 ksi).
  • the electrical conductivity of the alloy is preferably from about 45% to about 55% IACS.
  • the composition and processing provide a yield strength of from about 552 MPa (80 ksi) to about 690 MPa (100 ksi) and the electrical conductivity is between about 55% and about 65% IACS.
  • Fig. 1 illustrates in flow chart format, a process in accordance with a first embodiment of the invention. The alloy of the invention is melted and cast 10 in accordance with conventional practice.
  • the cast alloy is hot rolled 12 at from about 750°C to about 1 ,000°C. After milling to remove oxide, the alloy is then cold rolled 14 to a reduction in cross-sectional area transverse to the rolling direction ("reduction in area") of from about 50% to about 99%.
  • the alloy may then be solutionized 16 at a solution annealing temperature of from about 850 to about 1 ,000°C for from about 10 seconds to about one hour, followed by a quench 18 or rapid cool to ambient temperature to obtain equiaxed grains with an average grain size of about 5 and 20 ⁇ m. Thereafter the alloy may be first cold rolled 20 up to about 80% reduction in area, preferably about 30% to about 80% reduction in area.
  • the first cold roll 20 is followed by a first anneal 22 at a temperature of from about 400°C to about 650°C and preferably from about 450 °C to about 600°C for from about 1 minute to about 10 hours and preferably from about 1 to about 8 hours.
  • the alloy is then second cold rolled 24 from about a 10% to about a 50% reduction in area to finished gauge.
  • the second cold roll may be followed by a second anneal 26 at about 150°C to about 600°C and preferably from about 200°C to about 500°C for from about 15 seconds to about 10 hours.
  • the alloy is processed to finished gauge without using an in-process solutionizing heat treatment. That is, it can be processed to finish using cycles of lower temperature annealing treatments and intervening cold work.
  • This alternative process is especially useful for making a product with higher electrical conductivity levels.
  • Fig. 2 illustrates in flow chart representation an alternative process of the invention.
  • the alloy of the invention is melted and cast 10 in accordance with conventional practice.
  • the cast alloy is hot rolled 12 at from about 750°C to about 1 ,000°C. and then quenched or quickly cooled. After milling to remove oxide, the hot rolled alloy is then cold rolled 14 to a reduction in area of from about 50% to about 99%.
  • the alloy may then be first annealed 28 at an annealing temperature of from about 400°C to about 650°C for from about 15 sees, to about 10 hours.
  • the cold rolling and first annealing steps may optionally be repeated, if desired
  • the alloy is then cold rolled 30 from about 40% to about 80% reduction in area followed by a second anneal 32 at from about 400°C to about 650°C and preferably from about 450°C to about 600°C for from about 1 to about 10 hours.
  • the alloy is then cold rolled 34 from about a 10% to about a 50% reduction in area to finished gauge. This may optionally be followed by a third anneal 26 at about 150°C to about 600°C and preferably from about 200°C to about 500°C for from about 15 seconds to about 10 hours.
  • a second alternative preferred embodiment of the process of this invention employs an alloy in the preferred composition ranges.
  • This process is capable of making the alloy of this invention with nominal properties of about 758 MPa (110 ksi) YS and about 50% IACS conductivity.
  • the alloy is melted and cast 10 in accordance with conventional practice.
  • the cast alloy is hot rolled 12 at from about 750°C to about 1,000°C. After milling to remove oxide the hot rolled alloy is then cold rolled 14 to a reduction in area of from about 50% to about 99%.
  • the alloy is then solutionized 16 at a temperature of from about
  • the alloy is next cold rolled 20 to from about a 40% to about a 60% reduction in area and then first annealed 28 at about 400°C to about 650°C and preferably 450°C to about 600°C for from about 1 to about 10 hours and preferably from about 1 to about 3 hours.
  • the first anneal 28 is followed by cold rolling 30 from about a 40% to about a 60% reduction in area.
  • the alloy is then second annealed 32 at a lower temperature than the first anneal 28.
  • the second anneal is at a temperature of from about 375°C to about 550°C for from about 1 to about 3 hrs.
  • the doubly annealed alloy is then cold rolled 34 at least about 30% reduction in area to a finished gauge where it may be annealed a third time 26 at a temperature of from about 150°C to about 600°C and preferably from about 200°C to about 500°C for from about 1 to about 3 hours.
  • a series of 4.5 kg (ten pound) laboratory ingots with the analyzed compositions listed in Table 1 were melted in a silica crucible and Durville cast into steel molds. After gating the ingots were 10.16 cm x 10.16 cm x 4.45 cm (4"X4"X1.75"). After soaking for three hours at 950°C, the ingots were hot rolled in three passes to 2.8 cm (1.1"), reheated at 950°C for ten minutes, and further hot rolled in three passes to 1.27 cm (0.50”), followed by a water quench. The resultant hot rolled plates were homogenized by soaking for two hours at 1 ,000°C followed by a water quench.
  • the alloys were cold rolled to 1.27 mm (0.050"). The alloys were then solutionized at a temperature of 1000°C for from 20 to 60 seconds, with the exception of alloy J346 which was solutionized at 950°C for 60 seconds. Following solutionization and quenching, the alloys were cold rolled 50% to 0.64 mm (0.025") and age annealed at 550°C for 3 hours The alloys were then cold rolled 50% to 0.32 mm (0.0125”) gauge and relief annealed at 275°C for 2 hours and the properties reported in Table 2 measured.
  • the data in Table 2 show that high values of yield strength, from 621 MPa to 765 MPa (90 ksi to 111 ksi), and electrical conductivity, from 38.2% IACS to 63.8% IACS were obtained.
  • the stress relaxation resistance obtained was close to the desired value of 95% after 1000 hours at 105°C for the Cu-Ni-Ti-Fe alloys J345 and J346.
  • the desired value was achieved by the Cu-Ni-Ti-Mg alloy J354.
  • Example 2 In accordance with the process illustrated in Fig. 2, the alloys of Table 1 were processed as in Example 1 up through the homogenization heat treatment at hot rolled plate gauge. In this example, the alloys were processed to finish gauge without an in-process solutionizing heat treatment. After trimming and milling to remove the oxide coating, the alloys were cold rolled to 2.54 mm (0.100") and given a first aging anneal at 550°C for 3 hours. The alloys were then cold rolled 70% to 0.76 mm (0.030”) and subjected to a second aging anneal at 525°C for 3 hours. The alloys were then cold rolled 50% to 0.38 mm (0.015”) gauge and relief annealed 275°C for 2 hrs in which condition the properties recited in Table 3 were measured.
  • the alloys of this example had a combination of a high yield strength, from 676 MPa to 738 MPa (98 ksi to 107 ksi), but with higher electrical conductivity of between 49.9% IACS and 69.7% IACS.
  • Enhanced stress relaxation resistance is obtained when either Fe or Mg is added to the base Cu-Ni-Ti alloy.
  • the data in Table 3 show that the highest stress relaxation resistance obtained with a Mg addition to a Cu-Ni-Ti alloy; compare alloy J354 to alloy J351.
  • Example 3 In accordance with the process illustrated in Fig. 1 , a series of 4.5 kg (ten pound) laboratory ingots with the analyzed compositions listed in Table 4 were melted in silica crucibles and Durville cast into steel molds. After gating the ingots were 10.16 cm x 10.16 cm x 4.45 cm (4"X4"X1.75"). After soaking three hours at 950°C they were hot rolled in three passes to 2.8 cm (1.1") thick, reheated at 950°C / ten minutes, and further hot rolled in three passes to 1.27 cm (0.50") thick, followed by a water quench. After trimming and milling to remove the oxide coating, the alloys were cold rolled to 1.27 mm (0.050").
  • alloys other than J477 were then solution heat treated at 1 ,000°C for 25 seconds followed by a water quench to yield a controlled, fine, recrystallized grain size in the range 12 - 24 ⁇ m in diameter. Alloy J477 was solution heat treated at 950°C / 25 sees + WQ, yielding a grain size of 9 ⁇ m.
  • All alloys were then cold rolled 50% to 0.64 mm (0.025") thick and subjected to an aging anneal at 550°C for a time effective to maximize electrical conductivity without unduly softening the matrix. The times at 550°C are reported in Table 5. The alloys were then cold rolled 50% to 0.32 mm (0.0125”) gauge and relief annealed at 275°C for 2 hrs at which condition the properties in Table 5 were measured.
  • Example 4 IN accordance with the process illustrated in Fig. 2, the alloys of Table 4 were processed to finish gauge without using an in-process solutionizing heat treatment. After trimming and milling to remove the oxide coating, the alloys in the as hot rolled condition were cold rolled to 0.050" gauge and given a first aging anneal at a temperature and time as shown in Table 6 effective to maximize electrical conductivity. The alloys were then cold rolled 50% to 0.025" gauge and subjected to a second aging anneal at a temperature and time as shown in Table 6 selected to maximize the conductivity without unduly softening the matrix. The specific aging anneals applied to each alloy are noted in Table 6.
  • the alloys were then cold rolled 50% to 0.0125" gauge and relief annealed at 275°C for 2 hrs. at which condition the properties in Table 7 were measured. Using this process, the alloys with Fe and Mg additions provide lower, but still good, strength with higher electrical conductivity and good stress relaxation resistance.
  • the alloys were cold rolled to 2.54 mm (0.100") thick and solution heat treated in a furnace at 950°C for 40 seconds followed by a water quench to yield a controlled, fine, recrystallized grain size in the range 8.0 - 12 ⁇ m. They were then cold rolled 50% to 1.27 mm (0.050”) gauge and subjected to an aging anneal at 565°C for 3 hrs, designed to maximize the conductivity without unduly softening the matrix.
  • the alloys were then cold rolled 50% to 0.64 mm (0.025") gauge and given a second aging anneal of 410°C for 2 hrs, cold rolled to 0.25 mm (0.010"). This was followed by a relief anneal of 250°C for 2 hrs for which condition the properties in Table 9 were measured.
  • Comparing baseline alloy J694 to zirconium containing alloy J698 demonstrates that a small amount of zirconium increases the yield strength without affecting electrical conductivity.
  • a comparison of alloy J694 with silver containing alloy J699 demonstrates that a small amount of silver increases both the yield strength and the electrical conductivity.
  • a comparison of alloy J694 with chromium containing alloy J700 demonstrates that an addition of a small amount of chromium increases the yield strength slightly with a slight penalty in electrical conductivity.
  • Example 6 In accordance with the process illustrated in Fig. 3, a series of 4.5 (ten pound) laboratory ingots with the analyzed compositions listed in Table 10 were melted in silica crucibles and Durville cast into steel molds.
  • the ingots were 10.16 cm x 10.16 cm x 4.45 cm (4"X4"X1.75"). After soaking three hours at 950°C they were hot rolled in three passes to 2.8 cm (1.1") thick, reheated at 950°C for ten minutes, and further hot rolled in three passes to 1.27 cm (0.50”) thick, followed by a water quench. After trimming and milling to remove the oxide coating, the alloys were cold rolled to 2.54 mm (0.100") gauge and solution heat treated in a furnace at 1 ,000°C for 25-35 seconds followed by a water quench to yield a controlled, fine, recrystallized grain size in the range 6 - 12 ⁇ m.
  • Mg addition increases the yield strength ( and tensile strength) values over the Mg range: 0, 0.16, 0.25, 0.31 wt% Mg addition to: 703 (758), 710 (772), 745 (772), 745 (800), 758 (814) MPa [102 (110), 103 (112), 108 (116), 110 (118) ksi], respectively, at nearly constant conductivity values of about 48% IACS.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Conductive Materials (AREA)

Abstract

An age-hardening copper-base alloy and processing method to make a commercially useful strip product for applications requiring high yield strength and moderately high electrical conductivity, in a strip, plate, wire, foil, tube, powder or cast form. The alloys are particularly suited for use in electrical connectors and interconnections. The alloys contain Cu-Ti-X where X is selected from Ni, Fe, Sn, P, Al, Zn, Si, Pb, Be, Mn, Mg, Ag, As, Sb, Zr, B, Cr and Co. and combinations thereof. The alloys offer excellent combinations of yield strength, and electrical conductivity, with excellent stress relaxation resistance. The yield strength is at least of 724 MPa (105 ksi) and the electrical conductivity is at least 50% IACS.

Description

AGE-HARDENING COPPER-BASE ALLOY AND PROCESSING
This invention relates to an age-hardening copper-base alloy and a processing method to make commercially useful products from that alloy. More particularly, a copper alloy containing from 0.35% to 5%, by weight, titanium is wrought to finish gauge by a process that includes an in-process solution anneal and at least one age anneal. The resultant product has an electrical conductivity in excess of 50% IACS and a yield strength in excess of 724 MPa (105 ksi). Throughout this patent application, all compositions are in weight percent and all mechanical and electrical testing was performed at room temperature (nominally 22°C), unless otherwise specified. The word "about" implies ±10% and the word "base" as in copper-base, means the alloy contains at least 50%, by weight, of the specified base element. The terms "rolling" or "rolled" are intended to encompass drawing or drawn or any other form of cold reduction, for example, as used in the manufacture and processing of wire, rod or tubing.
Many different types of electrical connectors are formed from copper-base alloys. Properties important for an electrical connector include yield strength, bend formability, resistance to stress relaxation, modulus of elasticity, ultimate tensile strength and electrical conductivity.
Target values for these properties and the relative importance of the properties are dependent on the intended application of products manufactured from the subject copper alloys. The following property descriptions are generic for many intended applications, but the target values are specific for under the hood automotive applications.
The yield strength is the stress at which a material exhibits a specified deviation, typically an offset of 0.2%, from proportionality of stress and strain. This is indicative of the stress at which plastic deformation becomes dominant with respect to elastic deformation. It is desirable for copper alloys utilized as connectors to have a yield strength of at least 724 MPa. Stress relaxation becomes apparent when an external stress is applied to a metallic strip in service, such as when the strip is loaded after having been bent into a connector. The metal reacts by developing an equal and opposite internal stress. If the metal is held in a strained position, the internal stress will decrease as a function of both time and temperature. This phenomenon occurs because of the conversion of elastic strain in the metal to plastic, or permanent strain, by microplastic flow.
Copper based electrical connectors must maintain above a threshold contact force on a mating member for prolonged times for good electrical connection. Stress relaxation reduces the contact force to below the threshold leading to an open circuit. It is desirable for a copper alloy for connector applications to maintain at least 95% of the initial stress when exposed to a temperature of 105°C for 1000 hours and to maintain at least 85% of the initial stress when exposed to a temperature of 150°C for 1000 hours. The modulus of elasticity, also known as Young's modulus, is a measure of the rigidity or stiffness of a metal and is the ratio of stress to corresponding strain in the elastic region. Since the modulus of elasticity is a measure of the stiffness of a material, a high modulus, on the order of 140 GPa (20x103 ksi) is desirable. Bendability determines the minimum bend radius (MBR) which identifies how severe a bend may be formed in a metallic strip without fracture along the outside radius of the bend. The MBR is an important property for connectors where different shapes are to be formed with bends at various angles.
Bend formability may be expressed as, MBR/t, where t is the thickness of the metal strip. MBR/t is a ratio of the minimum radius of curvature of a mandrel about which the metallic strip can be bent without failure to the thickness of the strip. The "mandrel" test is specified in ASTM (American Society for Testing and Materials) designation E290-92, entitled Standard Test Method for Semi-Guided Bend Test for Ductility of Metallic Materials.
It is desirable for the MBR/t to be substantially isotropic, a similar value in the "good way", bend axis perpendicular to the rolling direction of the metallic strip, as well as the "bad way", bend axis parallel to the rolling direction of the metallic strip. It is desirable for the MBR/t to be about 1.5 or less for a 90° bend and about 2 or less for a 180° bend.
Alternatively, the bend formability for a 90° bend may be evaluated utilizing a block having a V-shaped recess and a punch with a working surface having a desired radius. In the "V-block" method, a strip of the copper alloy in the temper to be tested is disposed between the block and the punch and when the punch is driven down into the recess, the desired bend is formed in the strip.
Related to the V-block method is the 180° "form punch" method in which a punch with a cylindrical working surface is used to shape a strip of copper alloy into a 180° bend.
Both the V-block method and the form punch method are specified in ASTM designation B820-98, entitled Standard Test Method for Bend Test for Formability of Copper Alloy Spring Material.
For a given metal sample, both methods give quantifiable bendability results and either method may be utilized to determine relative bendability.
The ultimate tensile strength is a ratio of the maximum load a strip withstands before failure during a tensile test divided by the initial cross-sectional area of the strip. It is desirable for the ultimate tensile strength to be approximately 760 MPa. Electrical conductivity is expressed in % IACS (International Annealed
Copper Standard) in which unalloyed copper is defined as having an electrical conductivity of 100% IACS at 20°C.
Copper-base alloys containing titanium are disclosed in United States patent numbers 4,601 ,879 and 4,612,167, among others. The 4,601 ,879 patent discloses a copper-base alloy containing 0.25% to 3.0% of nickel, 0.25% to 3.0% of tin and 0.12% to 1.5% of titanium. Exemplary alloys have an electrical conductivity of between 48.5% and 51.4% IACS and a yield strength of between 568.8 MPa and 579.2 MPa (82.5 ksi and 84 ksi).
The 4,612,167 patent discloses a copper alloy containing 0.8% to 4.0% of nickel and 0.2% to 4.0% of titanium. Exemplary alloys have an electrical conductivity of 51% IACS and a yield strength of 663.3 MPa and 679.2 MPa (96.2 ksi to 98.5 ksi). AMAX Copper, Inc. (Greenwich, CT) has commercialized copper-nickel- titanium alloys having nominal compositions of Cu-2%Ni-1 %Ti and Cu-5%Ni- 2.5%Ti. The reported properties for the Cu-2%Ni-1 %Ti alloy are yield strength 441.3 MPa-551.6 MPa (64 - 80 ksi); ultimate tensile strength 503.3 MPa-655.0 MPa (73 - 95 ksi); elongation 9%; and electrical conductivity 50 - 60% IACS. The reported properties for the Cu-5%Ni-2.5%Ti alloy are yield strength 620.6 MPa- 689.5MPa (90 - 100 ksi); ultimate tensile strength 744.7 MPa (108 ksi) UTS; elongation 10 %; and electrical conductivity 40 - 53% IACS.
Many current and future applications for these copper alloys will require an electrical conductivity of at least 50% IACS and a yield strength of at least 724 MPa (105 ksi). There remains a need for copper-titanium alloys and processes for manufacturing the copper-titanium alloys capable of achieving the required levels of electrical conductivity and strength.
Summary Of The Invention
In accordance with the invention, there is provided an age-hardening copper-base alloy and methods to process this alloy to form a commercially useful product for any application requiring high yield strength and moderately high electrical conductivity. Typical forms for the product include strip, plate, wire, foil, tube, powder or cast form. The alloys when processed according to the methods of the invention achieve a yield strength of at least 724 MPa (105 ksi) and an electrical conductivity of 50% IACS making the alloys particularly suited for use in electrical connectors and interconnections.
The alloys consisting essentially of, by weight, from 0.35% to 5% titanium, from 0.001% to 10% of X, where X is selected from Ni, Fe, Sn, P, Al, Zn, Si, Pb, Be, Mn, Mg, Bi, S, Te, Se, Ag, As, Sb, Zr, B, Cr and Co and combinations thereof and the balance is copper and inevitable impurities. The alloy has an electrical conductivity of at least 50% IACS and a yield strength of at least 105 ksi..
In a preferred aspect of the invention, the alloy consists essentially of from 0.35% to 2.5% titanium, from 0.5% to 5.0% nickel, from 0.5% to 0.8% of iron, cobalt and mixtures thereof, from 0.01 % to 1.0% magnesium, up to 1 % of Cr, Zr, Ag and combinations thereof and the balance is copper and inevitable impurities. These alloys, when beryllium is not present, avoid the potentially dangerous health issues associated with current beryllium-copper alloys, while offering similar combinations of strength and conductivity.
Brief Description of the Several Drawings
Figure 1 illustrates in flow chart format a first method for processing the copper alloys of the invention.
Figure 2 illustrates in flow chart format a second method for processing the copper alloys of the invention. Figure 3 illustrates in flow chart format a third method for processing the copper alloys of the invention.
Detailed Description Of The Invention
Copper alloys having a combination of strength and electrical conductivity, as well as good formability and a resistance to stress relaxation are in demand for many electrical current carrying applications. Two exemplary applications are under-the-hood automotive applications and multimedia applications (such as computers, DVD players, CD readers and the like).
For automotive applications, there is a need for copper alloys with good formability, an electrical conductivity of at least 50% IACS and stress relaxation resistance up to 200°C. For multimedia interconnect applications, there is a need for copper alloys with a yield strength in excess of 724 MPa (105 ksi), an electrical conductivity in excess of 50% IACS and mechanical stability at room and slightly higher service temperatures, as characterized, by excellent stress relaxation resistance at about 100°C.
The alloy compositions when processed by the methods of this invention surprisingly provide an optimum combination of properties for meeting the needs for both automotive and multimedia applications, as well as other electrical and electronic applications. The alloys can provide moderately high strength along with high conductivity and moderately high conductivity along with very high strength.
The alloys of the present invention have compositions containing Cu-Ti-X, where X is selected from Ni, Fe, Sn, P, Al, Zn, Si, Pb, Bi, S, Te, Se, Be, Mn, Mg, Ag, As, Sb, Zr, B, Cr and Co and combinations thereof. The titanium content is from 0.35% to 5% and the sum total of the "X" elements is from 0.001 % to 10%.
Strength and electrical conductivity are maximized when X is selected from the group consisting of Ni, Fe, Co, Mg, Cr, Zr, Ag and mixtures thereof Oxygen, sulfur and carbon may be present in the alloys of the invention in amounts typically found in either electrolytic (cathode) copper or remelted copper or copper alloy scrap. Typically, the amount of each of these elements will be in the range of from about 2 ppm to about 50 ppm and preferably, each is present in an amount of less than 20 ppm. Other additions that influence the properties of the alloy may also be included. Such additions include those that improve the free machinability of the alloy, such as bismuth, lead, tellurium, sulfur and selenium. When added to enhance free machinability, these additions may be present in an amount of up to 2%. Preferably, the total of free machinability additions is between about 0.8% and 1.5%.
Typical impurities found in copper alloys, particularly in copper alloys formed from recycled or scrap copper, may be present in an amount of up to about 1%, in total. As a non-exclusive list, such impurities include magnesium, aluminum, silver, silicon, cadmium, bismuth, manganese, cobalt, germanium, arsenic, gold, platinum, palladium, hafnium, zirconium, indium, antimony, chromium, vanadium, and beryllium. Each impurity should be present in an amount of less than 0.35%, and preferably in an amount of less than 0.1%. It should be recognized that some of the above-recited impurities, or others, in amounts overlapping the above specified impurity ranges, may have a beneficial effect on the copper alloys of the invention. For example, strength or stampability may be improved. This invention is intended to encompass such low level additions.
In a more preferred embodiment of the invention, the titanium content is from 0.35% to 2.5% and in a most preferred embodiment, the titanium content is from 0.8% to 1.4%
When the titanium is in solution in the copper alloy matrix, electrical conductivity is severely degraded. Therefore, "X" should preferably be effective to cause titanium to precipitate from solution during an age anneal. Suitable elements for "X" to enhance such precipitation include Ni, Fe, Sn, P, Al, Si, S, Mg, Cr, Co and combinations of these elements.
One preferred addition is nickel. A combination of Ni and Ti provides precipitates of CuNiTi and the presence of Fe and Ti provides precipitates of Fe2Ti.
Another preferred addition is magnesium. An addition of Mg increases stress relaxation resistance and softening resistance in finished gauge and temper products. The Mg also provides softening resistance during in-process aging annealing heat treatments. When present at low levels, additions of Cr, Zr and/or Ag provide increased strengthening without unduly reducing conductivity.
One preferred alloy in accordance with the invention that has an improved combination of yield strength, electrical conductivity, stress relaxation resistance, along with modest levels of bendability consists essentially of about 0.5 - 5.0% Nickel about 0.35 - 2.5% Titanium about 0.5 - 0.8% Iron or Cobalt about 0.01 - 1.0% Magnesium, with optionally up to about 1.0% of one or more of Sn, P, Al, Zn, Si, Pb, Bi, S, Te, Se, Be, Mn, Mg, Ag, As, Sb, Zr, B, Cr and mixtures thereof, and the balance copper and impurities. Preferably the optional elements comprise up to 1% of one or more of Cr, Zr and Ag.
More preferred ranges for this alloy are: about 0.8 - 1.7% Nickel about 0.8 - 1.4% Titanium about 0.90 - 1.10% Iron, or Cobalt about 0.10 - 0.40% Magnesium, with up to about 1.0% of one or more of Cr, Zr, Ag or Sn and mixtures thereof, and the balance Copper and impurities In a first embodiment of the invention, the alloy composition and processing provide a yield strength of at least about 793 MPa (115 ksi) and preferably a yield strength of at least about 827 MPa (120 ksi). For this embodiment, the conductivity is up to about 40% IACS. In a second embodiment of the invention, the composition and processing provide a yield strength of more than about 724 MPa (105 ksi), and preferably up to about 793 MPa (115 ksi). In this second embodiment, the electrical conductivity of the alloy is preferably from about 45% to about 55% IACS. In a third embodiment, the composition and processing provide a yield strength of from about 552 MPa (80 ksi) to about 690 MPa (100 ksi) and the electrical conductivity is between about 55% and about 65% IACS. Fig. 1 illustrates in flow chart format, a process in accordance with a first embodiment of the invention. The alloy of the invention is melted and cast 10 in accordance with conventional practice. The cast alloy is hot rolled 12 at from about 750°C to about 1 ,000°C. After milling to remove oxide, the alloy is then cold rolled 14 to a reduction in cross-sectional area transverse to the rolling direction ("reduction in area") of from about 50% to about 99%. The alloy may then be solutionized 16 at a solution annealing temperature of from about 850 to about 1 ,000°C for from about 10 seconds to about one hour, followed by a quench 18 or rapid cool to ambient temperature to obtain equiaxed grains with an average grain size of about 5 and 20 μm. Thereafter the alloy may be first cold rolled 20 up to about 80% reduction in area, preferably about 30% to about 80% reduction in area. The first cold roll 20 is followed by a first anneal 22 at a temperature of from about 400°C to about 650°C and preferably from about 450 °C to about 600°C for from about 1 minute to about 10 hours and preferably from about 1 to about 8 hours. The alloy is then second cold rolled 24 from about a 10% to about a 50% reduction in area to finished gauge. The second cold roll may be followed by a second anneal 26 at about 150°C to about 600°C and preferably from about 200°C to about 500°C for from about 15 seconds to about 10 hours.
Alternatively in accordance with another embodiment, the alloy is processed to finished gauge without using an in-process solutionizing heat treatment. That is, it can be processed to finish using cycles of lower temperature annealing treatments and intervening cold work. This alternative process is especially useful for making a product with higher electrical conductivity levels. Fig. 2 illustrates in flow chart representation an alternative process of the invention. The alloy of the invention is melted and cast 10 in accordance with conventional practice. The cast alloy is hot rolled 12 at from about 750°C to about 1 ,000°C. and then quenched or quickly cooled. After milling to remove oxide, the hot rolled alloy is then cold rolled 14 to a reduction in area of from about 50% to about 99%. The alloy may then be first annealed 28 at an annealing temperature of from about 400°C to about 650°C for from about 15 sees, to about 10 hours. The cold rolling and first annealing steps may optionally be repeated, if desired The alloy is then cold rolled 30 from about 40% to about 80% reduction in area followed by a second anneal 32 at from about 400°C to about 650°C and preferably from about 450°C to about 600°C for from about 1 to about 10 hours. The alloy is then cold rolled 34 from about a 10% to about a 50% reduction in area to finished gauge. This may optionally be followed by a third anneal 26 at about 150°C to about 600°C and preferably from about 200°C to about 500°C for from about 15 seconds to about 10 hours.
A second alternative preferred embodiment of the process of this invention employs an alloy in the preferred composition ranges. This process is capable of making the alloy of this invention with nominal properties of about 758 MPa (110 ksi) YS and about 50% IACS conductivity. With reference to Fig. 3, the alloy is melted and cast 10 in accordance with conventional practice. The cast alloy is hot rolled 12 at from about 750°C to about 1,000°C. After milling to remove oxide the hot rolled alloy is then cold rolled 14 to a reduction in area of from about 50% to about 99%. The alloy is then solutionized 16 at a temperature of from about
950°C to about 1 ,000°C for from about 15 seconds to about 1 hour. The alloy is next cold rolled 20 to from about a 40% to about a 60% reduction in area and then first annealed 28 at about 400°C to about 650°C and preferably 450°C to about 600°C for from about 1 to about 10 hours and preferably from about 1 to about 3 hours. The first anneal 28 is followed by cold rolling 30 from about a 40% to about a 60% reduction in area. The alloy is then second annealed 32 at a lower temperature than the first anneal 28. The second anneal is at a temperature of from about 375°C to about 550°C for from about 1 to about 3 hrs. The doubly annealed alloy is then cold rolled 34 at least about 30% reduction in area to a finished gauge where it may be annealed a third time 26 at a temperature of from about 150°C to about 600°C and preferably from about 200°C to about 500°C for from about 1 to about 3 hours.
The alloys of the invention and the processes of the invention are better understood with reference to the Examples that follow.
Examples In the examples that follow some of the process descriptions, properties and units are written in an abbreviated form. For example, " = inches, WQ = water quench, a slash mark / = for, SA = solution anneal, CR = cold rolled or cold reduced, YS = yield strength, TS = tensile strength, EL = elongation, %IACS = electrical conductivity, MBR/t = minimum bend radius divided by the strip thickness, SR = stress relaxation resistance, Gs = grain size, μm = microns or micrometers, beg. = begin, recr. = recrystallized, n.c.r. = not completely recrystallized, sec. or s = seconds, hrs. or h = hours, MS/m = mega-siemens per meter and ksi thousands of pounds per square inch.
Example 1
Utilizing the process illustrated in Fig. 1 , a series of 4.5 kg (ten pound) laboratory ingots with the analyzed compositions listed in Table 1 were melted in a silica crucible and Durville cast into steel molds. After gating the ingots were 10.16 cm x 10.16 cm x 4.45 cm (4"X4"X1.75"). After soaking for three hours at 950°C, the ingots were hot rolled in three passes to 2.8 cm (1.1"), reheated at 950°C for ten minutes, and further hot rolled in three passes to 1.27 cm (0.50"), followed by a water quench. The resultant hot rolled plates were homogenized by soaking for two hours at 1 ,000°C followed by a water quench. After trimming and milling to remove oxide coating, the alloys were cold rolled to 1.27 mm (0.050"). The alloys were then solutionized at a temperature of 1000°C for from 20 to 60 seconds, with the exception of alloy J346 which was solutionized at 950°C for 60 seconds. Following solutionization and quenching, the alloys were cold rolled 50% to 0.64 mm (0.025") and age annealed at 550°C for 3 hours The alloys were then cold rolled 50% to 0.32 mm (0.0125") gauge and relief annealed at 275°C for 2 hours and the properties reported in Table 2 measured.
The data in Table 2 show that high values of yield strength, from 621 MPa to 765 MPa (90 ksi to 111 ksi), and electrical conductivity, from 38.2% IACS to 63.8% IACS were obtained. The stress relaxation resistance obtained was close to the desired value of 95% after 1000 hours at 105°C for the Cu-Ni-Ti-Fe alloys J345 and J346. The desired value was achieved by the Cu-Ni-Ti-Mg alloy J354.
Example 2 In accordance with the process illustrated in Fig. 2, the alloys of Table 1 were processed as in Example 1 up through the homogenization heat treatment at hot rolled plate gauge. In this example, the alloys were processed to finish gauge without an in-process solutionizing heat treatment. After trimming and milling to remove the oxide coating, the alloys were cold rolled to 2.54 mm (0.100") and given a first aging anneal at 550°C for 3 hours. The alloys were then cold rolled 70% to 0.76 mm (0.030") and subjected to a second aging anneal at 525°C for 3 hours. The alloys were then cold rolled 50% to 0.38 mm (0.015") gauge and relief annealed 275°C for 2 hrs in which condition the properties recited in Table 3 were measured.
Consistent with the data in Table 2, the alloys of this example had a combination of a high yield strength, from 676 MPa to 738 MPa (98 ksi to 107 ksi), but with higher electrical conductivity of between 49.9% IACS and 69.7% IACS. Enhanced stress relaxation resistance is obtained when either Fe or Mg is added to the base Cu-Ni-Ti alloy. The data in Table 3 show that the highest stress relaxation resistance obtained with a Mg addition to a Cu-Ni-Ti alloy; compare alloy J354 to alloy J351.
Example 3 In accordance with the process illustrated in Fig. 1 , a series of 4.5 kg (ten pound) laboratory ingots with the analyzed compositions listed in Table 4 were melted in silica crucibles and Durville cast into steel molds. After gating the ingots were 10.16 cm x 10.16 cm x 4.45 cm (4"X4"X1.75"). After soaking three hours at 950°C they were hot rolled in three passes to 2.8 cm (1.1") thick, reheated at 950°C / ten minutes, and further hot rolled in three passes to 1.27 cm (0.50") thick, followed by a water quench. After trimming and milling to remove the oxide coating, the alloys were cold rolled to 1.27 mm (0.050").
The alloys other than J477 were then solution heat treated at 1 ,000°C for 25 seconds followed by a water quench to yield a controlled, fine, recrystallized grain size in the range 12 - 24 μm in diameter. Alloy J477 was solution heat treated at 950°C / 25 sees + WQ, yielding a grain size of 9 μm.
All alloys were then cold rolled 50% to 0.64 mm (0.025") thick and subjected to an aging anneal at 550°C for a time effective to maximize electrical conductivity without unduly softening the matrix. The times at 550°C are reported in Table 5. The alloys were then cold rolled 50% to 0.32 mm (0.0125") gauge and relief annealed at 275°C for 2 hrs at which condition the properties in Table 5 were measured. The data in Table 5 show that, while the base alloy J477 offers a good combination of properties 634 MPa (92 ksi) YS and 58.1% IACS conductivity), the Fe addition increases the strength of the base alloy (J483 versus J477) to 690 MPa (100 ksi) with only a slight reduction in electrical conductivity. Moreover, the advantage of the Mg addition, while maintaining consistent amounts of Ni, Ti and Fe, for increasing stress relaxation resistance at 105°C is shown by comparing alloy J491 to J481. The advantage of Mg is also shown by comparison of the properties of alloy J491 (Table 5) compared to those of J345 and J346 in Table 2.
Example 4 IN accordance with the process illustrated in Fig. 2, the alloys of Table 4 were processed to finish gauge without using an in-process solutionizing heat treatment. After trimming and milling to remove the oxide coating, the alloys in the as hot rolled condition were cold rolled to 0.050" gauge and given a first aging anneal at a temperature and time as shown in Table 6 effective to maximize electrical conductivity. The alloys were then cold rolled 50% to 0.025" gauge and subjected to a second aging anneal at a temperature and time as shown in Table 6 selected to maximize the conductivity without unduly softening the matrix. The specific aging anneals applied to each alloy are noted in Table 6. The alloys were then cold rolled 50% to 0.0125" gauge and relief annealed at 275°C for 2 hrs. at which condition the properties in Table 7 were measured. Using this process, the alloys with Fe and Mg additions provide lower, but still good, strength with higher electrical conductivity and good stress relaxation resistance.
Example 5
In accordance with the process illustrated in Fig. 3, a series of 4.5 kg (ten pound) laboratory ingots with the analyzed compositions listed in Table 8 were melted in silica crucibles and Durville cast into steel molds After gating the ingots were 10.16 cm x 10.16 cm x 4.45 cm (4"X4"X1.75"). After soaking three hours at 950°C they were hot rolled in three passes to 2.8 cm (1.1") thick, reheated at
950°C for ten minutes, and further hot rolled in three passes to 1.27 cm (0.50") gauge, followed by a water quench. After trimming and milling to remove the oxide coating, the alloys were cold rolled to 2.54 mm (0.100") thick and solution heat treated in a furnace at 950°C for 40 seconds followed by a water quench to yield a controlled, fine, recrystallized grain size in the range 8.0 - 12 μm. They were then cold rolled 50% to 1.27 mm (0.050") gauge and subjected to an aging anneal at 565°C for 3 hrs, designed to maximize the conductivity without unduly softening the matrix. The alloys were then cold rolled 50% to 0.64 mm (0.025") gauge and given a second aging anneal of 410°C for 2 hrs, cold rolled to 0.25 mm (0.010"). This was followed by a relief anneal of 250°C for 2 hrs for which condition the properties in Table 9 were measured.
Comparing baseline alloy J694 to zirconium containing alloy J698 demonstrates that a small amount of zirconium increases the yield strength without affecting electrical conductivity. A comparison of alloy J694 with silver containing alloy J699 demonstrates that a small amount of silver increases both the yield strength and the electrical conductivity. A comparison of alloy J694 with chromium containing alloy J700 demonstrates that an addition of a small amount of chromium increases the yield strength slightly with a slight penalty in electrical conductivity. Example 6 In accordance with the process illustrated in Fig. 3, a series of 4.5 (ten pound) laboratory ingots with the analyzed compositions listed in Table 10 were melted in silica crucibles and Durville cast into steel molds. After gating the ingots were 10.16 cm x 10.16 cm x 4.45 cm (4"X4"X1.75"). After soaking three hours at 950°C they were hot rolled in three passes to 2.8 cm (1.1") thick, reheated at 950°C for ten minutes, and further hot rolled in three passes to 1.27 cm (0.50") thick, followed by a water quench. After trimming and milling to remove the oxide coating, the alloys were cold rolled to 2.54 mm (0.100") gauge and solution heat treated in a furnace at 1 ,000°C for 25-35 seconds followed by a water quench to yield a controlled, fine, recrystallized grain size in the range 6 - 12 μm. They were then cold rolled 50% to 1.27 mm (0.050") gauge and subjected to an aging anneal at 550 - 600°C for 3 - 4 hrs. The alloys were then cold rolled 50% to 0.64 mm (0.025") gauge and again given an aging anneal 410 - 425°C for 2 hrs, followed by cold rolling to 0.25 mm (0.010") and relief annealing at 250 - 275°C for 2 hrs.
The properties at finished gauge, listed in Table 11 , show a better yield strength and conductivity combination was obtained with either a Mg addition (J604 compared to J603) and/or a Zr addition (J644 compared to J603). Without the Mg addition, a Cr addition is not as effective by itself (Compare the low strengths of J646 in Table 11 (column D) with the higher strengths of J700 in Table 9). Note also from Table 11 how the Mg addition increases the yield strength ( and tensile strength) values over the Mg range: 0, 0.16, 0.25, 0.31 wt% Mg addition to: 703 (758), 710 (772), 745 (772), 745 (800), 758 (814) MPa [102 (110), 103 (112), 108 (116), 110 (118) ksi], respectively, at nearly constant conductivity values of about 48% IACS.
Example 7
This example illustrates how the composition and processing influences yield strength and electrical conductivity. Alloys J694 and J709 having the compositions recited in Table 12 were processed from 10.16 cm x 10.16 cm x 4.45 cm (4"x4"x1.75") ingots by soaking for 3 hours at 950°C and hot rolling to 1.27 cm (0.50 inch) followed by a water quench. After trimming and milling to remove oxides, the alloys were cold rolled to 2.54 mm (0.10 inch) and solution heat treated at 1000°C for 35 seconds and water quenched. The alloys were then cold rolled to 1.27 mm (0.05 inch), solutionized at 950°c for 35 seconds and water quenched. Further processing is as in Table 13 with properties recited in Table 14.
Table 12
Table 13
One or more embodiments of the present invention have been describe above. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.

Claims

WHAT IS CLAIMED:
1. A copper base alloy consisting essentially of, by weight: from 0.35% to 5% titanium; from 0.001% to 10% of X, where X is selected from Ni, Fe, Sn, P, Al, Zn,
Si, Pb, Be, Mn, Mg, Bi, S, Te, Se, Ag, As, Sb, Zr, B, Cr and Co and combinations thereof; and the balance copper and inevitable impurities, said alloy having an electrical conductivity of at least 50% IACS and a yield strength of at least 724 (105 ksi).
2. The copper base alloy of claim 1 characterized in that X is selected from the group consisting of Ni, Fe, Co, Mg, Cr, Zr, Ag and combinations thereof.
3. The copper base alloy of claim 2 further consisting essentially of: from 0.35% to 2.5% titanium; from 0.5% to 5.0% nickel; from 0.5% to 0.8% of iron, cobalt and mixtures thereof; from 0.01% to 1.0% magnesium; up to 1 % of Cr, Zr, Ag and combinations thereof; and the balance copper and inevitable impurities.
4. The copper base alloy of claim 3 further consisting essentially of: from 0.8% to 1.4% titanium; from 0.8% to 1.7% nickel; from 0.9% to 1.1% of iron, cobalt and mixtures thereof; from 0.1% to 0.4% magnesium; up to 1 % of Cr, Zr, Ag and combinations thereof; and the balance copper and inevitable impurities.
5. A copper base alloy having an improved combination of yield strength, electrical conductivity, stress relaxation resistance consisting essentially of by weight of:
0.35 - 2.5% titanium; 0.5 - 5.0% nickel;
0.5 - 1.5% iron, cobalt and mixtures thereof;
0.01 - 1.0% magnesium; up to 1% of Sn, Cr, Zr, Ag, Sn, P, Al, Zn, Si, Pb, Bi, S, Te, Se, Be, Mn, As, Sb, Zr, B and mixtures thereof; and the balance copper and inevitable impurities.
6 The copper base alloy of claim 5 containing up to 1 % of Cr, Zr, Ag and mixtures thereof.
7. The copper base alloy of claim 6 consisting essentially of
0.8 - 1.4% titanium;
0.8 - 1.7% nickel;
0.90 - 1.10% iron, or cobalt;
0.10 - 0.40% magnesium; 0.01 % to 1.0% of Cr, Zr, Ag and mixtures thereof; and the balance copper and inevitable impurities
8. A process for making a copper base alloy having an improved combination of yield strength, electrical conductivity and stress relaxation, characterized by: casting (10) a copper base alloy that consists essentially, by weight, from 0.35% to 10% titanium, from 0.001 % to 6% of X, where X is selected from Ni, Fe, Sn, P, Al, Zn, Si, Pb, Be, Mn, Mg, Bi, S, Te, Se, Ag, As, Sb, Zr, B, Cr and Co and combinations thereof and the balance copper and inevitable impurities; hot rolling (12) the alloy at from about 750°C to about 1,000°C; first cold rolling (14) the alloy to a reduction in area of from about 50% to about 97%; first annealing (16) the alloy at a temperature of from about 850°C to about
1 ,000°C for from about 10 seconds to about one hour, followed by a rapid cool (18) to ambient; second cold rolling (20) the alloy up to about 80% reduction in area; second annealing (22) the alloy at from about 400°C to about 650°C for from about 1 minute to about 10 hours; third cold rolling (24) the alloy from about a 10% to about a 50% reduction in area to finished gauge.
9. The process of claim 8 characterized in that following said third cold rolling step (24), said alloy is annealed (26) at a temperature of from about 150°C to about 600°C for from about 15 seconds to about 10 hours.
10. The process of claim 9 characterized in that said first (16), second (22) and third (26) annealing steps have times and temperatures effective for said alloy to have a yield strength of at least 724 MPa (105 ksi) and an electrical conductivity of at least 50% IACS at finish gauge.
11. A process for making a copper base alloy having an improved combination of yield strength, electrical conductivity, stress relaxation resistance, along with modest levels of bendability characterized by: casting (10) a copper base alloy that consists essentially, by weight, from 0.35% to 10% titanium, from 0.001 % to 6% of X, where X is selected from Ni, Fe, Sn, P, Al, Zn, Si, Pb, Be, Mn, Mg, Bi, S, Te, Se, Ag, As, Sb, Zr, B, Cr and Co and combinations thereof and the balance copper and inevitable impurities; hot reducing (12) the alloy at from about 750°C to about 1 ,000°C; providing one or more cycles comprising cold reducing (14) the alloy to a reduction in area of from about 50% to about 99% and then age annealing (28) at an annealing temperature of from about 400°C to about 650°C for from about 15 sees, to about 10 hours; cold reducing (30) the alloy from about 40% to about 80% reduction in area; age hardening (32) the alloy by annealing at from about 400°C to about
650°C for from about 1 to aboutlO hours; and final reducing (34) the alloy from about a 10% to about a 50% reduction in area to finished gauge.
12. The process of claim 11 characterized in that following said final cold rolling step (34), said alloy is annealed (26) at a temperature of from about 150°C to about 600°C for from about 15 seconds to about 10 hours.
13. The process of claim 12 characterized in that said annealing steps (28, 32, 26) have times and temperatures effective for said alloy to have a yield strength of at least 724 MPa (105 ksi) and an electrical conductivity of at least 50% at finish gauge.
14. A process for making a copper base alloy having high yield strength and moderate strength, electrical conductivity characterized by: casting (10) a copper base alloy that consists essentially, by weight, from 0.35% to 10% titanium, from 0.001% to 6% of X, where X is selected from Ni, Fe, Sn, P, Al, Zn, Si, Pb, Be, Mn, Mg, Bi, S, Te, Se, Ag, As, Sb, Zr, B, Cr and Co and combinations thereof and the balance copper and inevitable impurities; hot reducing (12) the alloy at from about 750°C to about 1 ,000°C; cold reducing (14) the alloy to a reduction in area of from about 50% to about 99%; solution annealing (16) the alloy at a temperature of from about 950°C to about 1 ,000°C for from about 15 seconds to about one hour, followed by a rapid cool to ambient; cold reducing (20) the alloy from about 40% to about a 60% reduction in area; age annealing (28) the alloy at a temperature of about 400°C to about
650°C for from about 1 to about 10 hours; cold reducing (30) the alloy from about a 40% to about a 60% reduction in area; age annealing (32) the alloy a second time at a lower temperature than the first aging anneal of from about 375°C to about 550°C for from about 1 to about 3 hours; and cold reducing (34) at least about 30% reduction in area to a finished gauge.
15. The process of claim 14 characterized in that following said final cold rolling step (34), said alloy is annealed (26) at a temperature of from about 150°C to about 600°C for from about 15 seconds to about 10 hours.
16. The process of claim 15 characterized in that said first (16), second (32) and third (26) annealing steps have times and temperatures effective for said alloy to have a yield strength of at least 724 MPa (105 ksi) and an electrical conductivity of at least 50% IACS at finish gauge.
17. A process for making a copper base alloy having high yield strength and moderate strength, electrical conductivity characterized by: casting (10) a copper base alloy that consists essentially, by weight, from 0.35% to 10% titanium, from 0.001 % to 6% of X, where X is selected from Ni, Fe, Sn, P, Al, Zn, Si, Pb, Be, Mn, Mg, Bi, S, Te, Se, Ag, As, Sb, Zr, B, Cr and Co and combinations thereof and the balance copper and inevitable impurities; hot rolling (12) the alloy at from about 750°C to about 1 ,000°C; cold rolling (14) the alloy to a reduction in area of from about 50% to about 99%; solution annealing (16) the alloy at a temperature of from about 950°C to about 1 ,000°C for from about 10 seconds to about one hour, followed by a rapid cool (18) to ambient; cold rolling (20) the alloy from about a 40% to about a 60% reduction in area; age annealing (28) the alloy at a temperature of about 500°C to about 575°C for from about 15 seconds to about 10 hours or at a temperature of about 425 to about 475°C for about 2.5 to about 3.5hours; cold rolling (30) the alloy from about a 40% to about a 60% reduction in area; age annealing (32) the alloy a second time at a temperature of from about 500°C to about 550°C for from about 1 to about 4 hours; and final rolling (34) at least about 30% reduction in area to a finished gauge.
18. The process of claim 17 characterized in that following said final cold rolling step (34), said alloy is annealed (26) at a temperature of from about 150°C to about 600°C for from about 15 seconds to about 10 hours.
19. The process of claim 18 characterized in that said annealing steps (16, 28, 32, 26) have times and temperatures effective for said alloy to have a yield strength of at least 724 MPa (105 ksi) and an electrical conductivity of at least 50% at finish gauge.
EP03754452.5A 2002-09-13 2003-09-05 Age-hardening copper-base alloy Expired - Lifetime EP1537249B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US41059202P 2002-09-13 2002-09-13
US410592P 2002-09-13
PCT/US2003/027856 WO2004024964A2 (en) 2002-09-13 2003-09-05 Age-hardening copper-base alloy and processing

Publications (3)

Publication Number Publication Date
EP1537249A2 true EP1537249A2 (en) 2005-06-08
EP1537249A4 EP1537249A4 (en) 2007-07-11
EP1537249B1 EP1537249B1 (en) 2014-12-24

Family

ID=31994162

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03754452.5A Expired - Lifetime EP1537249B1 (en) 2002-09-13 2003-09-05 Age-hardening copper-base alloy

Country Status (10)

Country Link
US (1) US20040166017A1 (en)
EP (1) EP1537249B1 (en)
JP (2) JP4590264B2 (en)
KR (1) KR20050050654A (en)
CN (1) CN1688732B (en)
AU (1) AU2003272276A1 (en)
CA (1) CA2497819A1 (en)
MX (1) MXPA05002640A (en)
TW (1) TW200422410A (en)
WO (1) WO2004024964A2 (en)

Families Citing this family (71)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4332889B2 (en) * 2003-05-30 2009-09-16 住友電気工業株式会社 Method for producing magnesium-based alloy compact
EP2626444A3 (en) * 2003-12-25 2013-10-16 JX Nippon Mining & Metals Corporation Copper or copper alloy target/copper alloy backing plate assembly
DE102005063324B4 (en) * 2005-05-13 2008-02-28 Federal-Mogul Wiesbaden Gmbh & Co. Kg Slide bearing composite, use and manufacturing process
KR20080027910A (en) * 2005-08-03 2008-03-28 닛코 킨조쿠 가부시키가이샤 High Strength Copper Alloys and Electronic Components for Electronic Components
JP5355865B2 (en) * 2006-06-01 2013-11-27 古河電気工業株式会社 Copper alloy wire manufacturing method and copper alloy wire
JP5520438B2 (en) * 2006-09-05 2014-06-11 古河電気工業株式会社 Wire manufacturing method and wire manufacturing apparatus
JP4563480B2 (en) * 2008-11-28 2010-10-13 Ｄｏｗａメタルテック株式会社 Copper alloy sheet and manufacturing method thereof
US8349724B2 (en) * 2008-12-31 2013-01-08 Applied Materials, Inc. Method for improving electromigration lifetime of copper interconnection by extended post anneal
JP4889801B2 (en) * 2009-11-25 2012-03-07 Ｊｘ日鉱日石金属株式会社 Manufacturing method of titanium copper for electronic parts
JP5464352B2 (en) * 2010-03-05 2014-04-09 三菱マテリアル株式会社 Method for producing high purity copper processed material having uniform and fine crystal structure
JP4672804B1 (en) * 2010-05-31 2011-04-20 Ｊｘ日鉱日石金属株式会社 Cu-Co-Si based copper alloy for electronic materials and method for producing the same
CN101956098B (en) * 2010-06-08 2011-12-28 上海华篷防爆科技有限公司 Titanium alloy explosion-proof material suitable for aerospace field and preparation method thereof
CN101892400A (en) * 2010-06-30 2010-11-24 天津大学 Copper-silver-titanium-tin oxide composite electrical contact material and preparation method thereof
CN101974702B (en) * 2010-07-28 2011-10-12 上海华篷防爆科技有限公司 Zinc-copper alloy explosionproof material and preparation method thereof
JP4834781B1 (en) 2010-08-24 2011-12-14 Ｊｘ日鉱日石金属株式会社 Cu-Co-Si alloy for electronic materials
JP5226057B2 (en) * 2010-10-29 2013-07-03 Ｊｘ日鉱日石金属株式会社 Copper alloys, copper products, electronic components and connectors
JP5611773B2 (en) * 2010-10-29 2014-10-22 Jx日鉱日石金属株式会社 Copper alloy, copper-drawn article, electronic component and connector using the same, and method for producing copper alloy
JP5226056B2 (en) * 2010-10-29 2013-07-03 Ｊｘ日鉱日石金属株式会社 Copper alloys, copper products, electronic components and connectors
US9181606B2 (en) 2010-10-29 2015-11-10 Sloan Valve Company Low lead alloy
CN102346000A (en) * 2011-06-27 2012-02-08 苏州方暨圆节能科技有限公司 Copper alloy material of radiator heat pipe
JP5380621B1 (en) * 2013-03-25 2014-01-08 Ｊｘ日鉱日石金属株式会社 Copper alloy sheet with excellent conductivity and stress relaxation properties
JP5427971B1 (en) * 2013-03-25 2014-02-26 Ｊｘ日鉱日石金属株式会社 Copper alloy sheet with excellent conductivity and bending deflection coefficient
KR101510222B1 (en) * 2013-03-29 2015-04-08 한국기계연구원 A copper alloy having high strength and high electrical conductivity
CN103456385B (en) * 2013-09-04 2016-01-20 江西理工大学 A kind of high-strength highly-conductive Cu-Cr-Ti alloy lead wire and preparation method thereof
JP5470499B1 (en) * 2013-09-25 2014-04-16 Ｊｘ日鉱日石金属株式会社 Copper alloy plate, high-current electronic component and heat dissipation electronic component including the same
JP2015086452A (en) * 2013-11-01 2015-05-07 株式会社オートネットワーク技術研究所 Copper alloy wire, copper alloy twisted wire, covered electric wire, wire harness, and copper alloy wire manufacturing method
CN103667771A (en) * 2013-12-03 2014-03-26 江苏帕齐尼铜业有限公司 Copper-magnesium alloy and preparation method thereof
CN103740976B (en) * 2014-01-16 2016-01-20 九星控股集团有限公司 By White Copper Tubes and preparation method thereof in a kind of oceanographic engineering
KR101468959B1 (en) * 2014-05-13 2014-12-08 한국기계연구원 A copper alloy having high strength and high electrical conductivity
CN104404292A (en) * 2014-11-13 2015-03-11 无锡信大气象传感网科技有限公司 High-strength copper alloy material for sensor and manufacture method
CN104505136A (en) * 2014-12-22 2015-04-08 乐清市长虹电工合金材料有限公司 Ceramic-shaped niobium copper hard special copper-based alloy electrical contact and preparation method thereof
CN104404295A (en) * 2014-12-25 2015-03-11 春焱电子科技（苏州）有限公司 Copper alloy for electronic material
CN104681145B (en) * 2015-02-04 2017-05-17 国网山东省电力公司日照供电公司 cable for computer
CN104674054A (en) * 2015-03-12 2015-06-03 天津理工大学 High-strength copper-titanium alloy and preparation method thereof
JP6031548B2 (en) * 2015-03-27 2016-11-24 株式会社神戸製鋼所 Copper alloy plate for heat dissipation parts
KR20170132146A (en) * 2015-04-01 2017-12-01 후루카와 덴끼고교 가부시키가이샤 Manufacturing method of flat rolled copper foil, flexible flat cable, rotary connector and flat rolled copper foil
CN104911390A (en) * 2015-06-13 2015-09-16 陈新棠 Antimicrobial corrosion-resistant heat exchanger copper tube
CN105040036B (en) * 2015-06-17 2017-07-28 中南大学 A kind of preparation method of non-ferrous metal electrodeposition calendering anode
CN105132734A (en) * 2015-07-13 2015-12-09 南通长江电器实业有限公司 High-strength and high-electric-conductivity copper alloy material
CN108018458A (en) * 2015-12-02 2018-05-11 芜湖楚江合金铜材有限公司 copper alloy wire processing method
CN105438637A (en) * 2015-12-24 2016-03-30 常熟市新冶机械制造有限公司 Morgan line bundling machine
JP6075490B1 (en) 2016-03-31 2017-02-08 株式会社オートネットワーク技術研究所 Shield wire for communication
DE112016006665T5 (en) * 2016-03-31 2018-12-20 Autonetworks Technologies, Ltd. communication cable
CN105925834A (en) * 2016-05-10 2016-09-07 安徽九华金润铜业有限公司 Anti-corrosion copper molybdenum chromium alloy
CN105925833A (en) * 2016-05-10 2016-09-07 安徽九华金润铜业有限公司 Cold-resistant copper chromium zirconium alloy
CN106191725B (en) * 2016-06-24 2018-01-26 河南江河机械有限责任公司 High-intensity high-conductivity copper alloy nanometer phase precipitation technique method
CN106222484A (en) * 2016-07-20 2016-12-14 合肥恒研智能科技有限公司 A kind of built-in industrial control machine housing high-strength alloy
RU2623512C1 (en) * 2016-10-10 2017-06-27 Юлия Алексеевна Щепочкина Copper-based alloy
WO2018143350A1 (en) * 2017-02-01 2018-08-09 株式会社オートネットワーク技術研究所 Electric wire for communication
CN110869525B (en) * 2017-07-14 2021-07-20 株式会社自动网络技术研究所 Covered wires and wires with terminals
US10872711B2 (en) * 2017-08-01 2020-12-22 Sumitomo Electric Industries, Ltd. Cable having a twisted pair electronic wire and a release layer
CN108642419A (en) * 2018-05-31 2018-10-12 太原晋西春雷铜业有限公司 A kind of corson alloy band and preparation method thereof that bending is excellent
KR101883627B1 (en) * 2018-06-08 2018-07-31 주식회사 지.에이.엠 Copper alloy and copper alloy casting expressing gold color
WO2020041925A1 (en) * 2018-08-27 2020-03-05 湖南特力新材料有限公司 Lead-free superhard self-lubricating copper alloy and manufacturing method therefor
JP6629401B1 (en) * 2018-08-30 2020-01-15 Ｊｘ金属株式会社 Titanium copper plate before aging treatment, pressed product and method for producing pressed product
CN109112353A (en) * 2018-10-29 2019-01-01 九江中船消防设备有限公司 A kind of titanium microalloying silicon brass alloy bar and preparation method thereof
JP6650987B1 (en) 2018-11-09 2020-02-19 Ｊｘ金属株式会社 Titanium copper foil, brass products, electronic equipment parts and autofocus camera modules
CN111378890A (en) * 2018-12-27 2020-07-07 杭州朱炳仁文化艺术有限公司 Cast copper sculpture material and preparation process of cast copper sculpture
KR102914491B1 (en) * 2019-04-12 2026-01-16 마테리온 코포레이션 Copper alloy having high strength and high conductivity and method for producing such copper alloy
CN110512115B (en) * 2019-09-29 2021-08-17 宁波金田铜业(集团)股份有限公司 High-strength and high-elasticity conductive copper-titanium alloy rod and preparation method thereof
CN111020277B (en) * 2019-12-11 2021-02-26 江西理工大学 A Cu-Fe-Co-Ti alloy with high electrical conductivity, softening resistance and stress relaxation resistance
CN111020278A (en) * 2019-12-14 2020-04-17 常州市申鑫新材料科技有限公司 Superfine high-precision copper alloy composite material
CN111041270A (en) * 2019-12-30 2020-04-21 南通南平电子科技有限公司 High-stability high-efficiency vehicle-mounted capacitor guide pin
CN111719065B (en) * 2020-06-08 2021-11-16 广东中发摩丹科技有限公司 Cu-Ni-Sn-Si-Ag-P multi-element alloy foil and preparation method thereof
CN112048637B (en) * 2020-09-15 2021-09-14 杭州铜信科技有限公司 Copper alloy material and manufacturing method thereof
CN112458332B (en) * 2020-10-13 2022-01-11 宁波博威合金材料股份有限公司 Titanium bronze alloy bar and preparation method and application thereof
CN112725655B (en) * 2020-12-23 2021-12-17 无锡日月合金材料有限公司 High-strength high-conductivity copper-chromium alloy for high-power device and preparation method thereof
CN113403499A (en) * 2021-06-01 2021-09-17 西安工程大学 Conductive elastic Cu-Ti-Ni-V alloy and preparation method thereof
CN115011823B (en) * 2022-06-28 2023-04-18 沈阳有色金属研究所有限公司 Processing method of Cu-Ni-Sn alloy product
CN116497297A (en) * 2023-05-05 2023-07-28 镇江大全金属表面处理有限公司 A processing technology of high flexibility copper soft conductor
CN120776164A (en) * 2025-07-29 2025-10-14 郑州新云锦特导新材料有限公司 High-strength high-plasticity superfine copper alloy wire, preparation method and application

Family Cites Families (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1991162A (en) * 1929-02-28 1935-02-12 Metal & Thermit Corp Process for improving coppertitanium alloys
US3201234A (en) * 1961-09-25 1965-08-17 Beryllium Corp Alloy and method of producing the same
JPS5853059B2 (en) * 1979-12-25 1983-11-26 日本鉱業株式会社 Precipitation hardening copper alloy
JPS60114542A (en) * 1983-11-22 1985-06-21 Ngk Insulators Ltd Age hardenable titanium-copper alloy material
US4612167A (en) * 1984-03-02 1986-09-16 Hitachi Metals, Ltd. Copper-base alloys for leadframes
DE3432226C1 (en) * 1984-06-07 1985-08-22 Wieland-Werke Ag, 7900 Ulm Copper-nickel-tin-titanium alloy, process for their production and their use
US4780275A (en) * 1984-08-25 1988-10-25 William Prym-Werke Gmbh. & Co. Kg. Corrosion-resistant copper alloy and article containing the same
US4678720A (en) * 1985-01-04 1987-07-07 Gte Laboratories Incorporated Silver-copper-titanium brazing alloy
JPS6250428A (en) * 1985-08-29 1987-03-05 Furukawa Electric Co Ltd:The Copper alloy for electronic appliance
US4606889A (en) * 1985-11-07 1986-08-19 Cabot Corporation Copper-titanium-beryllium alloy
JPS62263942A (en) 1986-05-09 1987-11-16 Hitachi Metals Ltd Copper alloy for lead frame
JPS63274728A (en) * 1987-05-01 1988-11-11 Dowa Mining Co Ltd Copper alloy for wire-harness terminal and its production
DE3820203A1 (en) * 1988-06-14 1989-12-21 Kabelmetal Ag USE OF A CURABLE copper alloy
JP2689507B2 (en) * 1988-08-10 1997-12-10 三菱マテリアル株式会社 Cu alloy terminal and connector materials
JPH02173248A (en) * 1988-12-26 1990-07-04 Nippon Mining Co Ltd Manufacture of copper alloy improved in adhesive strength of oxide film
JPH0315217A (en) * 1989-06-09 1991-01-23 Kinki Denki Kk Bird damage preventive tool for wire or the like
JPH04231447A (en) * 1990-12-27 1992-08-20 Nikko Kyodo Co Ltd Conductive material
JP2904372B2 (en) * 1991-10-08 1999-06-14 恒昭 三川 Age hardening special copper alloy
DE69317323T2 (en) * 1992-05-08 1998-07-16 Mitsubishi Materials Corp Wire for electrical railway line and method for producing the same
US5306465A (en) * 1992-11-04 1994-04-26 Olin Corporation Copper alloy having high strength and high electrical conductivity
US5370840A (en) * 1992-11-04 1994-12-06 Olin Corporation Copper alloy having high strength and high electrical conductivity
US5486244A (en) * 1992-11-04 1996-01-23 Olin Corporation Process for improving the bend formability of copper alloys
JPH06330211A (en) * 1993-05-27 1994-11-29 Kobe Steel Ltd Heat resistant copper alloy
US5338374A (en) * 1993-07-26 1994-08-16 The United States Of America As Represented By The Secretary Of The Navy Method of making copper-titanium nitride alloy
US5759548A (en) * 1993-11-30 1998-06-02 Lxr Biotechnology Inc. Compositions which inhibit apoptosis, methods of purifying the compositions and uses thereof
DE4438485C2 (en) * 1994-10-28 1998-05-20 Wieland Werke Ag Use of a copper-zinc alloy for drinking water installations
US5681662A (en) * 1995-09-15 1997-10-28 Olin Corporation Copper alloy foils for flexible circuits
US5882442A (en) * 1995-10-20 1999-03-16 Olin Corporation Iron modified phosphor-bronze
DE19548124C2 (en) * 1995-12-21 2002-08-29 Euroflamm Gmbh Friction body and method for producing such
JPH09263864A (en) * 1996-03-26 1997-10-07 Kobe Steel Ltd Copper alloy excellent in electric-discharge wear resistance
US6001196A (en) * 1996-10-28 1999-12-14 Brush Wellman, Inc. Lean, high conductivity, relaxation-resistant beryllium-nickel-copper alloys
US5865910A (en) * 1996-11-07 1999-02-02 Waterbury Rolling Mills, Inc. Copper alloy and process for obtaining same
US5820701A (en) * 1996-11-07 1998-10-13 Waterbury Rolling Mills, Inc. Copper alloy and process for obtaining same
JP2898627B2 (en) * 1997-03-27 1999-06-02 日鉱金属株式会社 Copper alloy foil
US5853505A (en) * 1997-04-18 1998-12-29 Olin Corporation Iron modified tin brass
JPH1081927A (en) * 1997-05-07 1998-03-31 Mitsubishi Materials Corp Cu alloy terminal and connector materials
US5893953A (en) * 1997-09-16 1999-04-13 Waterbury Rolling Mills, Inc. Copper alloy and process for obtaining same
DE19756815C2 (en) * 1997-12-19 2003-01-09 Wieland Werke Ag Wrought copper alloy, process for producing a semi-finished product therefrom and its use
FR2780417B1 (en) * 1998-06-26 2004-04-09 Kobe Steel Ltd ALLOY HAVING ANTIBACTERIAL AND STERILIZING EFFECT
US6136104A (en) * 1998-07-08 2000-10-24 Kobe Steel, Ltd. Copper alloy for terminals and connectors and method for making same
JP4154100B2 (en) * 1999-12-17 2008-09-24 日鉱金属株式会社 Copper alloy for electronic materials having excellent surface characteristics and method for producing the same
JP4460037B2 (en) * 2000-07-21 2010-05-12 古河電気工業株式会社 Method of heat treatment of copper alloy for electrical connection member and copper alloy for electrical connection member
US6749699B2 (en) * 2000-08-09 2004-06-15 Olin Corporation Silver containing copper alloy
JP4729680B2 (en) * 2000-12-18 2011-07-20 Ｄｏｗａメタルテック株式会社 Copper-based alloy with excellent press punchability
JP2002226928A (en) * 2001-01-30 2002-08-14 Nippon Mining & Metals Co Ltd Copper alloy foil for laminates

Also Published As

Publication number Publication date
KR20050050654A (en) 2005-05-31
TW200422410A (en) 2004-11-01
MXPA05002640A (en) 2005-07-19
AU2003272276A1 (en) 2004-04-30
CN1688732A (en) 2005-10-26
JP4590264B2 (en) 2010-12-01
WO2004024964A2 (en) 2004-03-25
AU2003272276A8 (en) 2004-04-30
CN1688732B (en) 2010-05-26
CA2497819A1 (en) 2004-03-25
JP2005539140A (en) 2005-12-22
JP2010275640A (en) 2010-12-09
WO2004024964A3 (en) 2004-07-01
EP1537249A4 (en) 2007-07-11
US20040166017A1 (en) 2004-08-26
EP1537249B1 (en) 2014-12-24

Similar Documents

Publication Publication Date Title
US20040166017A1 (en) Age-hardening copper-base alloy and processing
EP1179606B1 (en) Silver containing copper alloy
EP0203389B1 (en) Multipurpose copper alloys with moderate conductivity and high strength, and process for manufacturing them
US5370840A (en) Copper alloy having high strength and high electrical conductivity
US5601665A (en) Process for improving the bend formability of copper alloys
JP4809602B2 (en) Copper alloy
JPH0625388B2 (en) High strength, high conductivity copper base alloy
US4728372A (en) Multipurpose copper alloys and processing therefor with moderate conductivity and high strength
EP1063309A2 (en) Copper alloy
US5853505A (en) Iron modified tin brass
JP2790238B2 (en) Method for producing titanium copper alloy excellent in bending property and stress relaxation property
JPH09143597A (en) Copper alloy for lead frame and manufacturing method thereof

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050307

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1074648

Country of ref document: HK

DAX Request for extension of the european patent (deleted)
RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 9/06 20060101AFI20070307BHEP

Ipc: C22F 1/08 20060101ALI20070307BHEP

A4 Supplementary search report drawn up and despatched

Effective date: 20070611

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: WIELAND-WERKE AG

Owner name: GLOBAL METALS, LLC

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: GBC METALS, LLC

Owner name: WIELAND-WERKE AG

17Q First examination report despatched

Effective date: 20120810

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20141013

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 703176

Country of ref document: AT

Kind code of ref document: T

Effective date: 20150115

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60347140

Country of ref document: DE

Effective date: 20150219

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150325

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 703176

Country of ref document: AT

Kind code of ref document: T

Effective date: 20141224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60347140

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20150925

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1074648

Country of ref document: HK

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150905

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20150905

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20160531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150905

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150930

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150905

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20030905

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141224

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 60347140

Country of ref document: DE

Representative=s name: BAUR & WEBER PATENTANWAELTE PARTG MBB, DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20220922

Year of fee payment: 20

Ref country code: DE

Payment date: 20220608

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20220930

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 60347140

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MK

Effective date: 20230904