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EP3158095B1 - Kupfer-nickel-silizium-legierungen - Google Patents

Kupfer-nickel-silizium-legierungen Download PDF

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Publication number
EP3158095B1
EP3158095B1 EP08864853.0A EP08864853A EP3158095B1 EP 3158095 B1 EP3158095 B1 EP 3158095B1 EP 08864853 A EP08864853 A EP 08864853A EP 3158095 B1 EP3158095 B1 EP 3158095B1
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Prior art keywords
alloys
alloy
hours
yield strength
ksi
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French (fr)
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EP3158095A1 (de
EP3158095A4 (de
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Ralph A. Mutschler
Peter William Robinson
Derek E. Tyler
Andrea Kaufler
Hans Achim Kuhn
Uwe Hofmann
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Wieland Werke AG
GBC Metals LLC
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Wieland Werke AG
GBC Metals LLC
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • 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 copper base alloys, and in particular to copper-nickel-silicon base alloys.
  • Copper-nickel-silicon base alloys are widely used for the production of high strength, electrically conductive parts such as connectors and lead frames.
  • C7025 developed by Olin Corporation, is an important example of a copper-nickel-silicon base alloy that provides good mechanical (yield strength 95 ksi - 110 ksi / 655 MPa - 758 MPa) and good electrical properties (35% IACS). See U.S.Patent Nos. 4,594,221 and 4,728,372 , incorporated herein by reference.
  • C7035 a cobalt modified copper, nickel, silicon alloy
  • Olin Corporation and Wieland Werke which can provide even better mechanical (yield strength 100 ksi - 130 ksi / 689 MPa - 896 MPa) and electrical properties(40-55% IACS).
  • Yield strength 100 ksi - 130 ksi / 689 MPa - 896 MPa yield strength 100 ksi - 130 ksi / 689 MPa - 896 MPa
  • electrical properties 40-55% IACS
  • the properties of copper alloys that can be important include formability, conductivity, strength, ductility, and resistance to stress relaxation.
  • Formability is typically evaluated by a bend test where copper strips are bent 90°around a mandrel of known radiu s.
  • a roller bend test employs a roller to form the strip around the mandrel.
  • a v-block test uses the mandrel to push the strip into an open die, forcing it to conform to the radius of the mandrel.
  • the minimum bend radius is the smallest radius mandrel around which a strip can be bent without cracks visible at a magnification of 10x to 2Ox.
  • mbr/t is reported for both good way bends, defined as the bend axis is normal to the rolling direction, and for bad way bends, defined as the bend axis is parallel to the rolling direction.
  • An mbr/t of up to 4 t for both good way bends and bad way bends is deemed to constitute good formabiüty. More preferred is an mbr/t of up to 2.
  • IACS International Annealed Copper Standard that assigns "pure” copper a conductivity value of 100% IACS at 20°C T hroughout this disclosure, all electrical and mechanical testing is performed at room temperature, nominally 20° C, unless otherwise specified. The qualifying expression "about” indicates that exactitude is not required and should be interpreted as +/-10% of a recited value.
  • Strength is usually measured as yield strength.
  • a high strength copper alloy has a yield strength in excess of 95 ksi (655,1 MPa) and preferably in excess of 110 ksi (758,5 MPa). As the gauge of the copper alloy formed into components decreases and as miniaturization of these components continues, a combination of strength and conductivity for a given temper will be more important than either strength or conductivity viewed alone.
  • Ductility can be measured by elongation.
  • One measure of elongation is A10 elongation, which is the permanent extension of the gauge length after fracture, expressed as a percentage of the original gauge length Lo where Lo is taken equal to 10 mm.
  • Acceptable resistance to stress relaxation is viewed as at least 70% of an imparted stress remaining after a test sample is exposed to a temperature of 150°C for 3000 hours and at least 90% of an imparted stress remaining after a test sample is exposed to a temperature of 105°C for 1000 hours.
  • Stress relaxation may also be measured by a lift-off method as described in ASTM (American Society for Testing and Materials) Standard E328-86.
  • ASTM American Society for Testing and Materials
  • This test measures the reduction in stress in a copper alloy sample held at fixed strain for times up to 3000 hours.
  • the technique consists of constraining the free end of a cantilever beam to a fixed deflection and measuring the load exerted by the beam on the constraint as a function of time at temperature. This is accomplished by securing the cantilever beam test sample in a specially designed test rack.
  • the standard test condition is to load the cantilever beam to 80% of the room temperature 0.2% offset yield strength.
  • the initial stress is reduced until the deflection is less than 0.2 inch (5 mm) and the load is recalculated.
  • the test procedure is to load the cantilever beam to the calculated load value, adjust a threaded screw in the test rack to maintain the deflection, and locking the threaded screw in place with a nut.
  • the toad required to lift the cantilever beam from the threaded screw is the initial load.
  • the test rack is placed in a furnace set to a desired test temperature. The test rack is periodically removed, allowed to cool to room temperature, and the load required to lift the cantilever beam from the threaded screw is measured.
  • the percent stress remaining at the selected log times is calculated and the data are plotted on semi-log graph paper with stress remaining on the ordinate (vertical) and log time on the abscissa (horizontal). A straight line is fitted through the data using a linear regression technique. Interpolation and extrapolation are used to produce stress remaining values at 1, 1000, 3000, and 100,000 hours.
  • the resistance to stress relaxation is orientation sensitive and may be reported in the longitudinal (L) direction where 0°testing is conducted with the long dimension of the test sample in the direction of strip rolling and the deflection of the test sample is parallel to the strip rolling direction.
  • the resistance to stress relaxation may be reported in the transverse (T) direction where 90° testing is conducted with the long dimension of the test sample perpendicular to the strip rolling direction and the deflection of the test sample is perpendicular to the strip rolling direction.
  • Table 1 shows the mechanical and electrical properties of some of the commercially available copper alloys of which the inventors are aware: Table 1 Examples of properties of currently available Be-free Cu-based alloys Alloy Company Composition El. Conductivity (%IACS) Yield Strength, ksi C7025 Olin Brass Cu+3.0Ni+0.60Si+0.15Mg >35 95-110 EFTEC-75 Furukawa Cu+3.2Ni+0.65Si+0.5Zn+0.50Sn 25 116 EFTEC-23Z Furukawa Cu+2.5Ni+0.6Si+0.5Zn+0.03Ag 53 101-116 EFTEC-97 Furukawa Cu+2.3Ni+0.65Si+0.5Zn+0.15Sn+0.1Mg 40 110 EFTEC-98 Furukawa Unknown 38 104-136 EFTEC-98S Furukawa Cu+3.8Ni+0.93Si+0.48Zn+0.18Sn+0.13Mg+0.3Cr 38 95-129 K62 Wieland Cu+0.3Cf+
  • the copper based alloy and a method of making the copper based alloy according to the invention are given in the claims.
  • One aspect of the present invention is an age-hardening copper-nickel-silicon base alloy that can be processed to make a commercially useful strip product for use in electrical connectors and interconnections for the automotive and multimedia industries, in particular, and for any other applications requiring high yield strength and moderately high electrical conductivity in a strip, plate, wire or casting.
  • Another aspect of the present invention is a processing method to make a commercially useful strip product for use in electrical connectors and interconnections for the automotive and multimedia industries and any other applications requiring high yield strength and moderately high electrical conductivity.
  • This alloy is processed to have a yield strength of at least about 140 ksi (965 MPa), and an electrical conductivity of at least about 30% IACS.
  • the alloys are preferably processed to have a yield strength of at least about 143 ksi (986 MPa), and an electrical conductivity of at least about 37% IACS.
  • the ratio of (Ni+Co)/(Si-Cr/5) is preferably between about 3.5 and about 5.0.
  • the Ratio of Ni/Co is preferably between about 3 and about 5.
  • the alloys and processing methods of the various embodiments provide copper base alloys having an improved combination of yield strength and electrical conductivity, and preferably stress relaxation resistance as well.
  • the alloys have higher strength and greater resistance to stress relaxation than previously achieved with Cu-Ni-Si alloys, while maintaining reasonable levels of conductivity.
  • Alloys that are used for multimedia interconnects require high strength to avoid damage during connector insertion and to maintain good contact force while in service.
  • good but not especially high electrical conductivity is all that is required, since the conductivity merely needs to be enough to carry a signal current, and need not be the high levels needed to avoid excessive l 2 R heating in higher power applications.
  • alloy compositions of the preferred embodiments of this invention, and the scheme used to process to the finish tempers surprisingly provide highly desirable combination of properties for meeting the needs of both automotive and multimedia applications, namely very high strength along with moderately high conductivity, in particular, the alloys of the preferred embodiments of the present invention are capable of being processed to strip products with combinations of yield strength / electrical conductivity of at least about 140 ksi (965 MPa) with a conductivity of at least about 30% IACS.
  • the alloys of the preferred embodiment of the present invention have an improved combination of yield strength and electrical conductivity, good stress relaxation resistance, along with modest levels of bendability.
  • an optimum level of yield strength and electrical conductivity e.g. a combination of 140 ksi (965 MPa) YS / 30% IACS, the composition is given in claim 1.
  • excessive coarse second phases are present when alloying elements are substantially beyond the indicated upper limits.
  • the electrical conductivity and yield strength of the alloy are highest when the (Ni+Co)/(Si-Cr/5) ratio is controlled between about 3.5 and about 5.
  • the ratio of Ni/Co is optimal for yield strength and conductivity when controlled between about 3 and about 5.
  • Magnesium generally increases stress relaxation resistance and softening resistance in the finished products; it also increases softening resistance during in-process aging annealing heat treatments.
  • Sn When present at low levels, Sn generally provides solid solution strengthening and also increases softening resistance during in-process aging annealing heat treatments, without excessively harming conductivity.
  • Low levels of Mn generally improve bend formability, although with a loss of conductivity.
  • the preferred embodiment of the process of the present invention comprises melting and casting; hot rolling from 750° to 1050°C, optional milling to remove oxide, and an optional homogenization or intermediate bell anneal, cold rolling to a convenient gauge for solutionizing, solution annealing treatment at 800°- 1050°C for 10 seconds to one hour followed by a quench or rapid cool to ambient temperature to obtain an electrical conductivity of less than about 20% IACS (11.6 MS/m) and an equiaxed grain size of about 5-20 ⁇ m; a 0 to 75% cold rolling reduction in thickness; an age hardening anneal at 300 - 600°C from 10 minutes to 10 hours; and subsequently a further cold rolling 10 to 75% reduction in thickness to finish gauge; and second age hardening anneal at 250 to 500°C for 10 minutes to 10 hours.
  • the resulting alloy can also be processed to finish gauge without using an in-process solutionizing heat treatment by using cycles of lower temperature bel! annealing treatments with intervening cold work.
  • one or more optional recrystallization anneal(s) may be added to the process during the reduction from hot roiled gauge to the thickness appropriate for solutionizing.
  • the preferred scheme to result in alloy with a yield strength of at least about 140 ksi (965 MPa), and a conductivity of at least about 30% IACS conductivity involves solutionizing at about 900°t o 1000°C, cold rolling by about 25%, aging at about 450°- 500°C for 3 - 9 hours, c old rolling by about 20 - 25% to finish gauge, and aging 300°- 350°C for 3 -9 hours .
  • Fig. 1 is a flow chart of the process of this Example 1.
  • the alloys were cold rolled to 0.012" (0,3 mm) and solution heat treated in a fluidized bed furnace for the time and temperature listed in Table 2. Time and temperature were selected to achieve approximately constant grain size. The alloys were then subjected to an aging anneal of 400° to 500°C for 3 hours, designed to increase strength and conductivity. The alloys were then cold rolled 25% to 0.009" (0,23 mm) and aged at 300° to 400°C for 4 hours. Properti es measured after the second age anneal are presented in Table 3.
  • Ni/Co ratio of about 3 leads to a higher strength than a Nt/Co ratio of 1 (K001 and K003), particularly at the higher Si level.
  • Mn alloys K011 and K012 show evidence that Mn substitution for Ni improves the strength/bend properties, but at a significant loss of conductivity. Sn appears to provide solid solution strengthening, when comparing J994 to K036 and K037.
  • Fig. 2 is a flow chart of the process of this Example 2. Subsequently the alloys were cold rolled 25 % to 0.009" (0,23 mm) then subjected to an aging anneal of 400° to 500°C for 3 hours. After an additional cold reduction of 22% to 0.007" (0,18 mm), samples were aged annealed at temperatures of 300° to 400°C for 3 hours. Properties from representative conditions are listed in Table 4. Bend properties in many cases are somewhat better at similar strengths than the process in Example 1. Co (K003 and K004) and Sn (K037) additions provide the highest strength increase of the alloys in this example.
  • the alloys were then cold rolled to 0.012" (0,3 mm) and solution heat treated in a fluidized bed furnace for 60 seconds at the temperatures listed in Table 5. The temperature was selected to maintain a fairly constant grain size. Alloys were then subjected to an aging anneal of 400° to 500°C for 3 hours, designed to increase strength and conductivity. The alloys were then cold rolled 25% to 0.009" (0,23 mm) and aged at 300° to 400°C for 4 hours. Properties measured after the second age anneal are presented in Table 6.
  • Yield strength is plotted against conductivity in Figure 4 , and against bend formability in Figure 5 .
  • the values for K068, K070 and K072 are identified to show their unusually good combination of properties.
  • Table 5 Alloys of Examples 3 and 4 Alloy Analyzed composition, wt% ⁇ Ni+Co)/(Si-Cr/5)Ratio Ni/Co Solution Anneal Temperature Grain Size, ⁇ m K056 Cu - 4.94 Ni - 0.97 Si - 0.86 Sn 5.09 900°C 15 K057 Cu - 2.63 Ni - 0.73 Co - 0.80 Si - 0.88 Sn 4.20 3.60 925°C 16 K058 Cu - 3.80 Ni - 0.97 Co - 1.24 Si - 0.83 Sn 3.85 3.92 950°C 14 K059 Cu - 3.27 Ni - 0.82 Si - 0.22 Mn 3.99 850°C 20 K061 Cu - 3.83 Ni - 128 Co - 1.27 Si
  • Example 3 The alloys of Example 3 were solution heat treated in a fluidized bed furnace for 60 seconds at the temperature listed in Table 5.
  • Figure 6 is a flow chart of the process of this Example 4. Subsequently the alloys were cold rolled 25 % to 0.009" (0,23 mm) then subjected to an aging anneal of 400° to 500°C for 3 hours. After an additional cold reducti on of 22% to 0.007" (0,18 mm), samples were aged annealed at temperatures of 300° to 400°C for 3 hours. Properties from representative conditions are listed in Table 7. Similar to Example 3, of particular note are alloys K068, K070 and K072, which show that alloys containing Co, Cr or a combination of both achieve the highest strength levels.
  • the bend formability data indicates that K068 and K070 which both contain Co have the best formability at higher strength. Yield strength is plotted against conductivity in Figure 7 , and against bend formability in Figure 8 . The values for alloys K068, K070 and K072 are noted.
  • Figure 9 is a flow chart of the process of this Example 5. This group of alloys was based on K068, K070 and K072 from Table 5, wherein overall alloying level and Ni/Co ratio were varied while keeping the stoichiometric ratio ((Ni+Co)/(Si-Cr/5)) close to 4.2.
  • the alloys were then cold rolled to 0.012" (0,3 mm) and solution heat treated in a fluidized bed furnace for 60 seconds at the temperature listed in Table 8. The temperature was selected to maintain a fairly constant grain size. Alloys were then subjected to an aging anneal of 450° to 500°C for 3 hours, designed to increase strength and conductivity. The alloys were then cold rolled 25% to 0.009" (0,23 mm) and aged at 300 to 400°C for 4 hours. Properties measured after the second age anneal for the process with a 475°C first age and 300°C second age are presented in Table 9. For the Co-only set of compositions (K077 to K085), yield strength values tend to increase with higher alloying content.
  • K078, with a Ni+Co+Cr+Si value of 6.24 had a yield strength of 155 ksi (1069 MPa) while K084 with a Ni+Co+Cr+Si value of 5.22 had a 139 ksi (958 MPa) yield strength.
  • a Ni/Co ratio of 3 to 4 provides better strength than a ratio of 5, when one compares K077 (Ni/Co ratio of 3.62) and K078 (Ni/Co ratio of 3.83) to K079 (Ni/Co ratio of 5.04), as well as comparing K080 (Ni/Co ratio of 3.32) and K081 (Ni/Co ratio of 3.93) to K082 (Ni/Co ratio of 4.89).
  • the plots of yield strength vs Ni/Co ratio in Figure 10 illustrate this, with the exception of K085, which has a higher Si level than K083 and K084.
  • the Co-and-Cr-containing alloys, K086 to K094, were not as sensitive to overall alloying levels and Ni/Co ratio as the Co-only alloys.
  • the Cr-only alloys (K095 to K097) also had comparable properties to the other alloy types.
  • the alloys of Table 8 were solution heat treated in a fluidized bed furnace 60 seconds at the temperature listed in Table 8. Subsequently the alloys were cold rolled 25 % to 0.009" (0,23 mm) then subjected to an aging anneal of 450 to 500°C for 3 hours. After an additional cold reduction of 22% to 0.007" (0,18 mm), samples were aged annealed at temperatures of 300 to 400°C for 3 hours. Properties from samples given first and second ages at 450°C and 300°C, respectively, are listed in Table 10. The Co -only alloys displayed a sensitivity to overall alloying levels with this scheme which was not found in alloys containing Cr.
  • Figure 11 is a flow chart of the process of this Example 6.
  • the Ni-content is adjusted in order to keep a stoichiometric ratio ((Ni+Co)/(Si-Cr/5)) of close to 4.2.
  • the alloys After soaking two hours at 900°C they were hot rolled to 0.472" (12 mm), thereby reheated after each pass at 900°C for 10 mi nutes. After the last pass the bar was water quenched. After trimming and milling to 0.394" (10 mm) in order to remove the surface oxide, the alloys were cold rolled to 0.0106" (0,27 mm) and solution heat treated in a fluidized bed furnace for the time and temperature listed in Table 11. Time and temperature were selected to achieve grain sizes below 20 ⁇ m. The alloys were then subjected to an aging anneal of 450 to 500°C for 3 hours, designed to increase strength and conductivity.
  • the alloys were then cold rolled 25 % to 0.0079" (0,2 mm) and aged at 300 or 400°C for 3 hours. Properties measured after the second age anneal are presented in Table 12. The formability was measured via V-block. The data indicates that both alloys are capable of achieving a yield strength of 135 ksi (931 MPa), yet the Co-containing variant BS shows a better softening resistance that can be seen with increasing the age annealing temperature. The slightly better bad way bendability of variant BS is presumably due to the slightly lower grain size after solution annealing.
  • a group of alloys was cast and processed using once more the basic compositions of K068 (Co only), K070 (Co and Cr) and K072 (Cr only) from Table 5 as a base, but in this case with a gradual drop in Si levels, thus increasing the (Ni+Co)/(Si-Cr/5) stoichiometric ratio above the 3.6 to 4.2 range of previous alloys.
  • Ni and Co levels were designed to be constant for each of the three alloy types.
  • K143 to K146 are variants of K072
  • K160 to K163 variants of K070 and K164 to K167 are variants of K068.
  • Figure 12 is a flow chart of the process of this Example 7.
  • the alloys were then cold rolled to 0.012" (0,3 mm) and solution heat treated in a fluidized bed furnace for 60 seconds at the temperatures listed in Table 13. The temperature was selected to maintain a fairly constant grain size. The alloys were then cold rolled 25% to 0.009" (0,23 mm) and aged 450, 475 and 500°C for 3 hours. Properties aft er each aging temperature for alloys of the current example, as well as K068, K070, K072, K078, K087 and K089 are listed in Table 14. For each alloy type, yield strength decreases as the stoichiometric ratio increases above about 4.5, and falls below 120 ksi (827 MPa) at a ratio of around 5.5.
  • the alloys were then cold rolled to 0.012" (0,3 mm) and solution heat treated in a fluidized bed furnace for 60 seconds at 950°C. Grain size ranged from 6 to 12 ⁇ m. Alloys were then subjected to an aging anneal of 450 or 475°C for 3 hours, designed to increase strength and conductivity. The alloys were then cold rolled 25 % to 0.009" (0,18 mm) and aged at 300°C f or 4 hours. Properties measured after the second age anneal are presented in Table 16.
  • Table 17 has properties measured after samples were solution heat treated in a fluidized bed furnace for 60 seconds at 950°C, cold rolled 25% to 0.009" (0,23 mm), given an aging anneal at 475°C fo r 3 hours, cold rolled 22% to 0.007" (0,18 mm), and given a final anneal of 300°C for 3 hours.
  • the results show the viability of a range of compositions with Si from 1.0 to 1.2%, with a Ni/Co ratio of 4, and a stoichiometric ratio (((Ni+Co)/(Si-Cr/5))) of 3.5 to 5.0.
  • Figure 22 is a flow chart of the process of this Example 9.
  • the ingots were then machined to have tapered edges, as illustrated schematically in Figure 23 , to create a higher state of tensile stress at the edges. This condition is more prone to edge cracking than the standard flat edges, and thus more sensitive to alloying additions, in this case Cr.
  • the alloys were soaked for two hours at 900°C, and rolled in two passes to 1.12" (28,4 mm) (1.4" / 1.12") (35,6 mm / 28,4 mm) then water quenched. After examination for cracks, the bars were reheated at 900°C for two hours, and rolled in three passes to 0.50" (13 mm) (0.9" / 0.7" / 0.5") (23 mm / 18 mm / 13 mm), followed by a water quench. It was found that without Cr, K224 developed large cracks during the first few passes of hot rolling, which enlarged during the remaining passes. None of the Cr-containing alloys developed large cracks during hot roiling.
  • Table 21 lists the normalized casting plant yield (CPY) of six Cr-containing and four non-Cr bars, where the normalized CPY is obtained as follows: First the individualized CPY is calculated as the ratio of coil milled weight to cast bar weight. Second the bar with the highest CPY, in this case RN 033410, is assigned a normalized CPY of 100%. Third the normalized CPY of all other bars is calculated by dividing the CPY of each bar by the CPY of RN033410. The normalized CPY of bars without Cr is 48-82% compares to 82-100% for the Cr-containing bars.
  • CPY normalized casting plant yield
  • Figure 26A shows wear on a tool steel ball which was slid for 3000 linear inches (76 m) (1500 inches (38 m) on each side of the strip) under a 100 gm load over the strip surface with lard oil as a lubricant of a non-Cr sample (RN033407) that was plant solution annealed at 975°C, cold rolled 25% then aged a 450° C and sulfuric acid cleaned, while Figure 26B has a similar condition using a sample of a Cr-containing alloy (RN834062). The polished appearance of the ball shown in Fig.
  • FIG. 26 shows that the Cr-containing alloy caused much more wear, leading to a significantly larger volume of material being removed from the ball. This is seen in Fig. 26 as a much larger wear scar for the Cr-containing alloy. The larger wear scar suggests that during stamping of a sheet of the alloy into parts, a high amount of tool wear would occur.
  • a Single casting run produced three bars with the composition shown in Table 21a. Casting plant yield of the bars, which was normalized similarly to the data of Table 21 where RN033410 is considered 100%, is given in Table 21b.
  • the CPY of the low-Cr bars compares favorably with the Cr-containing bars of Table 21. This is believed to be due to Cr reducing cracking during hot rolling even at these low levels.
  • RN037969 has a normalized CPY% above 100 due to the fact that the yield of this bar was higher than RN033410 in the earlier example.
  • Table 21a Analyzed compositions of low-Cr bars cast and processed in the plant Bar Ni Co Cr Si Mg 037969 3.70 0.98 0.059 1.07 0.093 037970 037971 Table 21b Bar Type CPY% (normalized) RN037969 Low-Cr 102.1% RN037970 Low-Cr 89.8% RN037971 Low-Cr 68.4%
  • FIG. 27 is a flow chart of the process of this Example 10.
  • Alloy K259 contains a smaller level of Cr than those alloys in Example 9, to investigate the lower limits of the beneficial effect of Cr on hot rolling.
  • Alloys K251, K254 and K260 contain low levels of Mn, to determine if Mn affects hot rollability in the alloy of this invention. The ingots were then machined to have tapered edges, as illustrated schematically in Fig.
  • the quenched bars were then soaked at 590s C for 6 hours, trimmed and then milled to remove surface oxides developed during hot rolling.
  • the alloys were then cold rolled to 0.012" (0,3 mm) and solution heat treated in a fluidized bed furnace for 60 seconds at 950°C. Alloys were then subjected to an aging anneal of 475°C for 3 hours, designed to increase strength and conductivity.
  • the alloys were then cold rolled 25 % to 0,009" (0,23 mm) and aged at 300°C for 3 hours.
  • the alloys were cold rolled 25% to 0.009" (0,23 mm), given an aging anneal at 475°C for 3 hours, cold roiled 22% to 0.007" (0,18 mm), and given a final anneal of 300°C for 3 hours. Properties after the final age for both process paths are listed in Table 23. For both processes, the exceptionally good property combination of 150 ksi (1034 MPa) yield strength and at least 31 % IACS are achieved, with low levels of Cr, Mn or neither.
  • Process A involved cold rolling to 0.012" (0,3 mm) and solution heat treating in a fluidized bed furnace for 60 seconds at 950°C, age annealing at 500°C for 3 hours, cold roiling 25% to 0.009" (0,23 mm), and giving a second anneal at 350°C for 4 hours.
  • process BF the metal was rolled to 0.050" (1,3 mm) and given an intermediate bell anneal ("IMBA”) of 575°C for 8 hours.
  • IMBA intermediate bell anneal
  • the samples were subject to cold rolling to 0.012" (0,3 mm) and solution heat treating in a fluidized bed furnace for 60 seconds at 950°C, age annealing at 500°C for 3 hours, cold rolling 25% to 0.009" (0,23 mm), and giving a second anneal at 350°C for 4 hours.
  • process C the allo y was rolled to 0.024" (0,61 mm) and solution heat treated in a fluidized bed furnace for 60 seconds at 950°C, followed by cold rolling to 0.012" (0,3 mm) and a second solution heat treatment in a fluidized bed furnace for 60 seconds at 950°C.
  • process D age annealing at 500°C for 3 hours, cold rolling 25% to 0.009" (0,23 mm), and giving a second anneal at 350°C for 4 hours.
  • cold rolling to 0.012" (0,3 mm) was followed by solution heat treatment in a fluidized bed furnace for 60 seconds at 950°C the alloy was cold rolled 2 5% to 0.009" (0,23 mm), given an aging anneal at 475°C for 3 hours, cold rolled 22% to 0.007" (0,18 mm), and given a final anneal of 300°C for 3 hours.
  • proce ss E the metal was rolled to 0.050" (1,27 mm) and given an intermediate bell anneal of 575°C for 8 hours. Then the samples were rolled to 0.024" (0,61 mm) and solution heat treated in a fluidized bed furnace for 60 seconds at 950°C, foil owed by cold rolling to 0.012" (0,3 mm) and a second solution heat treatment in a fluidized bed furnace for 60 seconds at 950°C. Subsequently, the process involved age annealing at 500°C for 3 hours, cold rolling 25% to 0.009" (0,23 mm), and giving a second anneal at 350°C for 4 hours.
  • Figure 31 is a flow chart of the process of this Example 12. After cold rolling to 0.012" (0,3 mm), samples were solution annealed in a fluidized bed furnace at temperatures of 925, 950, 975 and 1000°C for 60 seconds. Coupons were then given age anneals at temperatures of 450, 475, 500 and 525°C for three hours. Samples we re then cold rolled to final thickness at varying reductions of 15, 25 and 35%.
  • Table 25 contains properties of samples with different solution anneal temperatures while the rest of the process was held constant. As solution temperature is increased, yield strength increases, while conductivity decreases. Additionally, bend formability worsens at the higher solution annealing temperatures, due to the large grain size developed during the 975 and 1000°C anneals. Thus a solution annealed grain size below 20 ⁇ m is preferred.
  • the temperature of the first age is varied while the other processing variables are held constant, it is found that the highest strength levels are due to the intermediate aging temperatures, as shown for the 475 and 500°C ages in Table 26. Also, the conductivity increased with increasing aging temperature. Thus the first age temperature can be manipulated to provide various desirable combinations of strength and conductivity.
  • Table 28 shows that the second age anneal temperature does not have a large effect on properties when the other processing variables are held constant. Conductivity was found to increase as the temperature of the second age increased, but to a small degree. Thus a wide operating range is acceptable for this step of the process.
  • Table 25 Effect of varying solution anneal temperatures, with 475°C first age, 25% roll reduction, 350°C second age of Example 12 SA temperature, °C SA grain size, ⁇ m YS/TS/EI %IACS 90° Bends 925 9.0 142.3/147.7/3 36.0 6.0/6.0 950 12.9 145.9/152.3/3 34.1 6.1/6.1 975 26.1 146.5/152.6/2 32.3 6.1/12.1 1000 28.8 147.5/152.1/3 32.7 8.7/12.1 Table 26 Effect of varying first age temperatures, with 950°C solution anneal, 25% roll reduction, 350° C second age of Example 12 1 st Age Temp, °C YS/TS/EI %IACS 90° Bends 450 140.1/145.2/4 30.5 4.0/6.1 475 145.9/152.3/3 34.1 6.1/6.1 500 145.1/152.7/3 36.2 4.0/7.0 525 133.2/134.5/1 39.9 n/m * *not measured Table 27 Effect of varying roll reductions,
  • Samples from the Cr-free plant-cast bar RN033407 (composition in Table 20) were rolled in the laboratory from the coil milled condition at 0.460" (11,7 mm) down to 0.012" (0,3 mm). Subsequently samples were solution heat treated in a fluidized bed furnace for 60 seconds at 900°C. Coupons were then rolled 25% to 0.009" (0,23 mm) and age annealed at 425, 450 and 475°C for times of 4 and 8 hours at each temperature. Subsequently samples were cold rolled 22% to 0.007" (0,18 mm) and given a final anneal of 300°C for three hours.
  • Figure 32 is a flow chart of the process of this Example 13. After soaking two hours at 900°C they were hot roll ed to 0.472" (12 mm), thereby reheated after each pass at 900°C for 10 minutes. After the last pass the bar was water quenched. After trimming and milling to 0.394" (10 mm) in order to remove the surface oxide, the alloys were cold rolled to 0.012" (0,3 mm) and solution heat treated in a fluidized bed furnace for the time and temperature listed in Table 29. Time and temperature were selected to achieve grain sizes below 20 ⁇ m.
  • the alloys were cold rolled 25 % to 0.009" (0,23 mm) then subjected to an aging anneal of 450 and 475°C for 3 hours.
  • Properties of samples are listed in Table 30.
  • the formability was measured via V-block. With increasing Si-content the yield strength is increasing from 121 ksi (834 MPa) for the 1.05% Si alloy to 135 ksi (931 MPa) for the 1.51% Si alloy. For the 1.16% Si variants Mg results in a benefit to yield strength of 5-7 ksi (34 - 48 MPa). Lowering the Ni/Co ratio from 11.37 to 4.98 enhances yield strength for the high Si (1.5%) alloys.
  • Table 31 shows the stress relaxation data for variants BV, BW and BX. Comparing BV and BW, due to Mg addition the stress relaxation resistance increases from 66.3% to 86.6% for the 150°C/1000 h condition and from 48.5% to 72.3% for the 200°C/1000 h condition. The stress relaxation resistance of the higher Si-containing BX amounts to 82.3% for the 150°C/1000 h condition and 68.7% for the 200°C/1000 h condition.
  • Figure 33 is a flow chart of the process of this Example 14. Specimens of Example 13 were subsequently cold rolled to 0.007" (0,18 mm) with a cold reduction of 22%. Thereafter the samples were aged annealed at temperatures of 300 °C to 400°C for 3 hours. Proper ties from samples given second ages at 300°C are listed in Table 32. The fo rmability was measured via V-block.
  • the stress relaxation resistance increases from 72.6% to 85.6% for the 150°C/1000 h condition and from 55.8% to 69.3% for the 200°C/1000 h condition.
  • the stress relaxation resistance of the higher Si-containing BX amounts to 81.1% for the 150°C/1000 h condition and 66.1% for the 200°C/1000 h condition.
  • the alloys were cold rolled 25 % to 0.009" (0,23 mm) then subjected to an aging anneal of 450 and 475°C for 3 hours. Properties of samples are listed in Table 35.
  • the yield strength, formability measured with V-block and conductivity of the Cr-free FL and FM are similar to the Cr-containing BV and BW from Example 13, with comparable Si-content of 1.1%, Ni/Co ratio and stoichiometric ratio.
  • an addition of 0.1 %Mg results in a benefit to yield strength of 7-8 ksi (48 - 55 MPa).
  • Table 36 shows the stress relaxation data for the processes with a solution annealing temperature of 950°C. Compared to the Cr-containing 1.16% Si samples of Example 13, BV and BW, the stress relaxation of FL and FM is slightly lower. Similar to Example 13, a Mg addition of 0.1% results in a stress relaxation increase from 64.6% to 82.7% for the 150°C/1000 h condition and from 44.3% to 69.2% for the 200°C/1000 h condition. The stress relaxation resistance of the Mg-containing, Si1.39% variant FN amounts to 84.1 % for the 150°C/1000 h condition an d 65.9% for the 200°C/1000 h condition.
  • Figure 35 is a flow chart of the process of this Example 16.
  • Specimens of Example 15 were subsequently cold roiled to 0.007" (0,18 mm) with a cold reduction of 22%. Thereafter the samples were aged annealed at temperatures of 300°C to 350°C for 3 hours. Properties from samples given second ages at 300°C are listed in Table 37. The fo rmability was measured via V-block. The highest yield strength was achieved with a first aging temperature of 450°C.
  • FM shows a higher yield strength of 11 ksi (76 MPa) in comparison to FL1 that is partly ascribed to the Mg-content and partly ascribed to the slightly higher Si-content.
  • the yield strength, bendability and conductivity of the Cr-free FL and FM are similar to the Cr-containing BV and BW from example 15, with comparable Si-content, Ni/Co ratio and stoichiometric ratio.
  • the stress relaxation resistance of the Mg-containing, Si 1.39% variant FN amounts to 85.0% for the 150°C/1000 h condition and 66.4% for the 200°C/1000 h condition.
  • Table 37 Properties from SA-C R-1AA-C R-2 A A Process of Example 16 Alloy SA-conditions 1.AA T, °C 2.AA 300°C/3h YS, ksi TS, ksi A10, % %IACS 90° MINBR/t GW/BW FL 950°C - 1 minute 450 133.1 140 2.7 31.6 4.5/6.1 475 129.7 139.5 1.9 36.2 3.9/4.4 FM 950°C - 1 minute 450 144 147.6 2 31 4.4/7.2 475 141.3 145 1.8 33.2 4.5/6.8 FN 950°C - 1 minute 450 143.2 150.0 2 31.5 3.9/7.2 475 133.1 138.9 2.4 34.3 3.3/5.6 1000°C - 1 minute 450 158.1
  • Figure 36 shows the relation between 90°-mi nBR/t BW and yield strength for the alloys and processes of Examples 13, 14, 15, and 16. Both processes SA-CR- AA and SA - CR - AA - CR - AA form two groups with a certain formability - yield strength relation.
  • the solid lines are just a guide to the eye and mark increasing Min BR/t and increasing yield strength with higher Si-content and/or Mg-addition. There is almost no difference in yield strength and formability - yield strength relationship between the Cr-containing and Cr-free variants.
  • Figure 37 shows the relation between %IACS and yield strength for the alloys and processes of Examples 13, 14, 15, and 16.
  • the Cr-free and the Cr-containing alloys show the same capability in achieving a conductivity of 30%iACS together with high yield strength.
  • the SA - CR - AA - CR - AA process achieves higher yield strength than the SA-CR- AA process, but at the same conductivity.

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Claims (4)

  1. Legierung auf Kupferbasis mit einer verbesserten Kombination aus Streckgrenze, elektrischer Leitfähigkeit und Spannungsrelaxationswiderstand, bestehend aus:
    zwischen 3,5 und 3,9 Gewichtsprozent Ni;
    zwischen 0,8 und 1,0 Gewichtsprozent Co;
    zwischen 1,0 und 1,2 Gewichtsprozent Si;
    zwischen 0,05 und 0,15 Gewichtsprozent Mg,
    bis zu 0,1 Gewichtsprozent Cr;
    bis zu 1,0 Gewichtsprozent Sn, und bis zu 1,0 Gewichtsprozent Mn,
    wobei der Rest aus Kupfer und Verunreinigungen besteht und das Verhältnis von Ni / Co zwischen 3 und 5 liegt,
    und wobei die Legierung derart bearbeitet wird, dass sie eine Streckgrenze von mindestens 140 ksi aufweist und die elektrische Leitfähigkeit mindestens 30% IACS beträgt.
  2. Legierung nach Anspruch 1, dadurch gekennzeichnet, dass das Verhältnis von (Ni+Co)/(Si-Cr/5) zwischen 3,5 und 5,0 liegt.
  3. Verfahren zur Herstellung einer Legierung auf Kupferbasis nach einem der vorhergehenden Ansprüche, umfassend folgende Schritte:
    Schmelzen und Gießen der Legierung;
    Warmwalzen von 750° auf 1050° C;
    Kaltwalzen auf ein geeignetes Maß zum Lösungsglühen;
    Lösungsglühen der Legierung zwischen 800° und 1050° C für 10 Sekunden bis zu einer Stunde; und
    anschließendes Abschrecken oder schnelles Abkühlen der Legierung auf Umgebungstemperatur, um eine elektrische Leitfähigkeit von weniger als 20% IACS (11,6 MS/m) und einer gleichachsigen Korngröße von 5 - 20 Mikrometer zu erhalten;
    Kaltwalzen der Legierung für eine Verringerung der Dicke um 0 bis 75%;
    Unterziehen der Legierung einer Härtungsglühung bei 300 ° bis 600 ° für 10 Minuten bis 10 Stunden;
    anschließendes Kaltwalzen der Legierung für eine Verringerung der Dicke um 10 bis 75% auf das Endmaß;
    Unterziehen der Legierung einem zweiten Aushärtungsglühen bei 250 bis 500 ° C für 10 Minuten bis 10 Stunden.
  4. Das Verfahren nach Anspruch 3, weiter umfassend ein Zwischenrekristallisationsglühen nach dem Warmwalzen.
EP08864853.0A 2007-12-21 2008-12-19 Kupfer-nickel-silizium-legierungen Not-in-force EP3158095B1 (de)

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US1644107P 2007-12-21 2007-12-21
US4490008P 2008-04-14 2008-04-14
US12/336,731 US20090183803A1 (en) 2007-12-21 2008-12-17 Copper-nickel-silicon alloys
PCT/US2008/087705 WO2009082695A1 (en) 2007-12-21 2008-12-19 Copper-nickel-silicon alloys

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JP5261161B2 (ja) * 2008-12-12 2013-08-14 Ｊｘ日鉱日石金属株式会社 Ｎｉ−Ｓｉ−Ｃｏ系銅合金及びその製造方法
WO2011036804A1 (ja) * 2009-09-28 2011-03-31 Jx日鉱日石金属株式会社 電子材料用Ｃｕ－Ｎｉ－Ｓｉ－Ｃｏ系銅合金及びその製造方法
CN102666889A (zh) * 2009-12-02 2012-09-12 古河电气工业株式会社 铜合金板材及其制造方法
WO2013099242A1 (en) * 2011-12-28 2013-07-04 Yazaki Corporation Ultrafine conductor material, ultrafine conductor, method for preparing ultrafine conductor, and ultrafine electrical wire
JP6154997B2 (ja) * 2012-07-13 2017-06-28 古河電気工業株式会社 強度およびめっき性に優れる銅合金材およびその製造方法
JP6154996B2 (ja) * 2012-07-13 2017-06-28 古河電気工業株式会社 高強度銅合金材およびその製造方法
JP5647703B2 (ja) 2013-02-14 2015-01-07 Ｄｏｗａメタルテック株式会社 高強度Ｃｕ−Ｎｉ−Ｃｏ−Ｓｉ系銅合金板材およびその製造法並びに通電部品
CN105264105B (zh) * 2013-06-04 2018-08-24 日本碍子株式会社 铜合金的制造方法及铜合金
JP2017089003A (ja) * 2015-11-03 2017-05-25 株式会社神戸製鋼所 放熱部品用銅合金板
DE102017001846A1 (de) 2017-02-25 2018-08-30 Wieland-Werke Ag Gleitelement aus einer Kupferlegierung
JP6600401B1 (ja) * 2018-10-11 2019-10-30 三芳合金工業株式会社 時効硬化型銅合金の製造方法
JP7215735B2 (ja) * 2019-10-03 2023-01-31 三芳合金工業株式会社 時効硬化型銅合金
WO2022139466A1 (ko) * 2020-12-23 2022-06-30 한국재료연구원 G-phase을 포함하는 구리-니켈-규소-망간 합금 및 이의 제조방법

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TWI461548B (zh) 2014-11-21
CN101939452A (zh) 2011-01-05
TW200936786A (en) 2009-09-01
WO2009082695A9 (en) 2009-09-24
KR20100120644A (ko) 2010-11-16
CA2710311A1 (en) 2009-07-02
US20090183803A1 (en) 2009-07-23
MX2010006990A (es) 2010-12-02
EP3158095A4 (de) 2017-04-26

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