MX2010006990A - Copper-nickel-silicon alloys. - Google Patents

Abstract

A copper base alloy having an improved combination of yield strength and electrical conductivity consisting essentially of between about 1.0 and about 6.0 weight percent Ni, up to about 3.0 weight percent Co, between about 0.5 and about 2.0 weight percent Si, between about 0.01 and about 0.5 weight percent Mg, up to about 1.0 weight percent Cr, up to about 1.0 weight percent Sn, and up to about 1.0 weight percent Mn, the balance being copper and impurities, the alloy processed to have a yield strength of at least about 137ksi, and an electrical conductivity of at least about 25% IACS.

Description

COPPER-NICKEL-SILICON ALLOYS BACKGROUND This invention relates to copper base alloys, and in particular to copper-nickel-silicon based alloys.

The copper-nickel-silicon based alloys are widely used for the production of electrically conductive, high-strength parts such as connectors and connection frames. C7025, developed by Olin Corporation, is an important example of a copper-nickel-silicon base alloy that provides good mechanical properties and good electrical properties (deformation resistance 95 ksi - 110 ksi) and (35% IACS). See U.S. Patent Nos. 4,594,221 and 4,728,372, incorporated herein by reference. More recently, C7035, an alloy of copper, nickel, silicon modified with cobalt, has been developed by Olin Corporation and Wieland Werke, which can provide even better mechanical properties (deformation resistance 100 ksi - 130 ksi) and electrical (40 -55% of IACS). See U.S. Patent No. 7,182,823, incorporated herein by reference.

The properties of copper alloys that may be important include formability, conductivity, strength, ductility, and resistance to stress relaxation.

The formability is typically evaluated by a bend test where the copper strips are bent 90 ° around a known radius mandrel. A roll bend test uses a roller to form the wrap around the mandrel. Alternatively, a block test in the form of using the mandrel to push the strip into an open mold, leading it to conform to the radius of the mandrel. For both tests the minimum bend radius (mbr) as a function of the thickness of the strip (t) is then reported as mbr / t. The minimum bend radius is the smallest radius of the mandrel around which a strip can bend without visible cracks of an increase from 10x to 20x. Generally mbr / t is reported for both bends in a good manner, defined as the bending axis which is normal to the direction of rolling, and for bending badly, defined as the bending axis which is parallel to the direction of the rolling . A mbr / t of up to 4 t for both bends in good way and bends in a bad way are considered to constitute good formability. More preferred is a mbr / t of up to 2.

Electrical conductivity is typically measured with a percentage of IACS guides. The IACS refers to the International Annealed Copper Standard that assigns "pure" copper a conductivity value of 100% IACS at 20 ° C. Throughout this description, all electrical and mechanical testing is Perform at room temperature, nominally at 20 ° C, unless otherwise specified. The qualifying expression "approximately" indicates that accuracy is not required and should be interpreted as +/- 10% of a quoted value.

The resistance is usually measured as deformation resistance. A high strength copper alloy has a strain resistance above 95 ksi (655.1 MPa) and preferably above 110 ksi (758.5 MPa). As the caliber of the copper alloy is formed into components it decreases and as the miniaturization of these components continues, a combination of strength and conductivity for a given tempering will be more important than any resistance or conductivity observed alone. : The ductility can be measured by elongation. An elongation measurement is an elongation A10 which is the permanent extension of the caliber length after the fracture, expressed as a percentage of the original caliber length Lo where Lo is taken equal to 10 mm.

The acceptable resistance to stress relaxation is observed as at least 70% of a given tension that remains after a test sample is exposed to a temperature of 150 ° C for 3000 hours and at least 90% of a imparted tension that remains after a test sample that is exposed to a temperature of 105 ° C for 1000 hours.

The stress relaxation resistance · was measured by the ring method [Fox A.: Research and Standards 4 (1964) 480] where a strip of 50. mm in length is clamped on the outer radius of a steel ring that starts the tension e 'the outer surface of the strip. With exposure to temperatures - high stresses, elastic change in plastic deformation. This process depends on the time, temperature and initial tension defined by the radius of the steel ring. Experiments were carried out between 50 ° C / 96h and 210 ° C / 384h. After each annealing the remaining bending of the strip 1 is measured and the corresponding voltage reduction is calculated according to [Graves G.B .: Wire Industry 46 (1979) 421]. Using the Larson-Miller P parameter, extrapolation from short-time experiments performed at higher temperatures to long-time experiments at lower temperatures can be done [Boegei A .: Metail 48 (1994) 872].

The stress relaxation can also be measured by a takeoff method as described in the ASTM Standard (American Society for Material Testing) E3'28-86. This test measures the reduction in tension in a sample of copper alloy held at a fixed voltage for times of up to 3000 hours. The technique consists in subjecting the free end of a cantilever beam to a fixed deflection and in measuring the load exerted by the beam of the subjection as one. function from time to temperature. This is achieved 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 resistance, of deviation deformation of 0.2% at room temperature. If the calculated deflection exceeds approximately 0.2 inches, the initial tension is reduced until the deflection is less than 0.2 and the load is recalculated. The test procedure is to load the cantilever beam to the calculated load value, fit a threaded screw in the test rack to maintain deflection, and fix the threaded screw in place with a nut. The load required to lift the cantilever beam from the threaded bolt is the initial load. The test rack is placed in an oven 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 percentage of tension that remains of the selected record times is calculated and the data is plotted on semi-logarithmic graph paper with tension remaining in the ordinate (vertical) and recording time in the abscissa (horizontal). A straight line fits through the data using a linear regression technique. Interpolation and extrapolation are used to produce remaining values of tension a 1, 1000, 3000 and 100,000 hours.

The resistance to stress relaxation is sensitive to orientation and can be reported in the longitudinal direction (L) where the test at 0 or is conducted with the long dimension of the test sample in the direction of the lamination of the strip and the deflection of the test sample is parallel to the rolling direction of the strip. The resistance to stress relaxation can be reported in the transverse direction (T) where the 90 ° test is conducted with the long dimension of the test sample perpendicular to the direction of strip lamination and the deflection of The test sample is perpendicular to the direction of the lamination of the strip.

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 alloys based on Cu without Be currently available Alloy Company Composition El, Resistance Conductivity of Deformation, (% of IACS) ksi C7025 Olín Brass CU + 3.0M + O.60SM) .15MD > 35 95-110 EFTEC-75 Furuka to CU + 3.2Ni + 0.65SI + 0.5ZrV 0.50Sn 25 116 EFTEC-23Z Furukawa Cu + 2.5N¡ + O.eSi + O.5Zn + 0.03Aq 53 101-118 EFTEC-97 Furukawa Cu + 2.3 I + 0.65SW) .SZiHO.16Sn + O.1 fl 40 110 EFTEC-98 Furukawa Unknown 38 104-138 EFTEC-98S Furukawa Cut3.8Ni + O.S3SW.48Zn + O.18Sn + 0.13 fl + 0.3Cr 38 95-129 K62 Wieland Cu + 0.3Cr40.4Ni + 0.6Sn + 0.03"n 62 100 KLF-125 Kobe Steel Cu + 3.2Ni + O.70Si + 0.3ZrHl 2BMn 35 100 CAC-65 Kobe Steel CU + 32NÍ + O.70SI + 1, 0Zn + 0.50Sn 45 94 MAX 251 Mitsubishi Cü + 2.QNi + 0.50Si + 0.50Sn 45 '| 89 Shindo Max375 Mitsubishi Cu + 2.85Ni O.7Si + O.5Zl > H) .5Sll + 0.015Ma 42 91-116 KLF-1 Kobe Steel Cu + 3.2N¡ + 0.70Si + 0.3Zr »0.05Mn 55 88 C7027 O! In Brass Cu + 2.0Ni + 0.60Si + O.60Fe + O.5OSn > 40 > 80 Cu + 0.5Cr4O.1Ap + O.O8Fe + 0.06TM.O3Si 80 80 C1807Q / 75 Wieland Cu + 0.3Cr + 0.1Tk0.02Si > 75 70 PMC 102 Poongaan CU + 1.3H + 0J.5SÍ + O.O5P 60 75 C7035 / K57 O! In / Wia! And Cu + 1.4NW .lCo 0.6SI > 45 110-130 NKC388 Nippon Mining Cu + 3.8Ni + 0.85Sf + 0.18Mq-0.1 Mn 35-45 112.125 HCL 305 Hitachi Cu + 2,5Ni + 0.5Sk17Zn + 0.02P 42 87-102 HCL 307 Hitachi CU + 3.0NÍ + 0.7SH-1.7Zn + 0.3SrHO.02P 35 102.112 As good as these alloys, and as widespread as their use, there are remaining applications where alloys with higher strength and in particular higher strength without sacrificing other desirable properties such as conductivity, resistance to stress relaxation, and / or formability. While beryllium coppers can provide high strength, due to their beryllium content, they are not suitable for many applications. Among beryllium-free copper alloys, high strength (eg, deformation strength above about 130 ksi) is usually accompanied by a significant decrease in other desirable properties, in particular formability.

SHORT DESCRIPTION One aspect of the present invention is an age-hardened copper-nickel-silicon base alloy that can be processed to be a commercially useful strip product for use in electrical connectors and interconnects for the automotive and multimedia industries, in particular, and for any other applications that require high deformation resistance and moderately high electrical conductivity in a strip, plate, wire or molded part. Another aspect of the present invention is a processing method for being a commercially useful strip product for use in electrical connectors and interconnections for the automotive and multimedia industries and any other applications that require high deformation resistance and moderately high electrical conductivity.

According to a preferred embodiment of this invention, a copper-nickel-silicon base alloy having an improved combination of strain resistance and electrical conductivity consisting essentially of between about 10 and about 6.0 weight percent is provided. of Ni, up to about 3.0 weight percent of. Co, between about 0.5 and about 2.0 percent by weight of Si, between about 0.01 and about 0.5 percent by weight of Mg, up to about 1.0 percent by weight of Cr, up to about 1.0 percent by weight of Sn, and up to about 1.0 percent by weight of Mn, the remainder being copper and impurities. This alloy is processed to have a deformation strength of at least about 137 ksi, and an electrical conductivity of at least about 32% IACS.

According to another preferred embodiment of this invention, a copper base alloy having an improved combination of strain resistance and electrical conductivity is provided consisting essentially of: between about 3.0 and about 5.0 weight percent Ni; up to approximately 2.0 percent in Co weight; between about 0.7 and about 1.5 weight percent Si; between about 0.03 and about 0.25 weight percent g; to about 0.6 weight percent Cr; up to about 1.0 weight percent Sn, and up to about 1.0 weight percent Mn, the remainder being copper and impurities. This alloy is processed to have a deformation strength of at least about 137 ksi, and an electrical conductivity of at least about 32% IACS.

According to another preferred embodiment of this invention, there is provided a copper-nickel-silicon base alloy having an improved combination of deformation resistance and electrical conductivity consisting essentially of: between about 3.5 and about 3.9 weight percent of Ni; between about 0.8 and about 1.0 weight percent of Co; between about 1.0 and about 1.2 weight percent Si; between approximately 0.05 and about 0.15 weight percent Mg; to about 0.1 weight percent Cr; up to about 1.0 weight percent Sn, and up to about 1.0 weight percent Mn, the remainder being copper and impurities. This alloy is processed to have a deformation strength of at least about 137 ksi, and an electrical conductivity of at least about 32% IACS.

The alloys are preferably processed to have a deformation strength of at least about 137 ksi, and an electrical conductivity of at least about 38% of IACS, more preferably having a deformation resistance of at least> 100 g. at least about 143 ksi, and an electrical conductivity of at least about 37% IACS, and most preferably have a strain resistance of at least about 157 ksi, and an electrical conductivity of at least about 32% IACS.

The ratio of (Ni + Co) / (Si-Cr / 5) is preferably between about 3 and about 7, and more preferably between about 3.5 and about 5.0. The Ni / Co ratio is preferably between about 3 and about 5.

The alloys and processing methods of the various modalities provide copper base alloys which have an improved combination of forming strength and electrical conductivity, and preferably deformation relaxation resistance as well. In particular, the alloys have higher strength and greater resistance to stress relaxation than those previously achieved with alloys of. Cu-Ni-Si, while maintaining reasonable levels of conductivity.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart of the treatment of the alloys in Example 1; Fig. 2 is a flow chart of the treatment of the alloys in Example 2; Fig. 3 is a flow chart of the treatment of the alloys in Example 3; Fig. 4 is a plot of the deformation resistance against the conductivity for the. alloys of Example 3; Fig. 5 is a graph of the deformation resistance against bending formability (MBR / t) for the alloys of Example 3; Fig. 6 is a flow chart of the treatment of the alloys of Example 4; Fig. 7 is a graph of the resistance of deformation against conductivity for the alloys of Table 5 processed by a process of SA-CR-aging-CR- aging of Example 4; FIG. 8 is a plot of the deformation resistance against bending formability (BR / t) for the alloys of Table 5 processed by the SA-CR-aging-CR-aging process of Example 4; Fig. 9 is a flow chart of the treatment of the alloys in Example 5; Fig. 10 is a graph of the strain resistance vs. Ni / Co ratio for the chromium-free alloys having similar alloy levels of Example 5; Fig. 11 is a flow chart of the treatment of the alloys in Example 6; Fig. 12 is a flow chart of the treatment of the alloys in Example 7; Fig. 13 is a graph showing the effect of the stoichiometric ratio on the strain resistance in the copper-nickel-chromium-silicon alloys of Example 7 '· Fig. 14 is a graph showing the effect of the stoichiometric ratio on the strain resistance in the copper-nickel-cobalt-silicon alloys of Example 7; :, Fig. 15 is a graph showing the effect of the stoichiometric ratio on the deformation resistance in the copper-nickel-chromium-cobalt-silicon alloys of the Example 7; Fig. 16 is a graph showing the effect of the stoichiometric ratio on the electrical conductivity in copper-nickel-chromium-silicon alloys of Example 7; FIG. 17 is a graph showing the effect of the stoichiometric ratio on the electrical conductivity in copper-nickel-cobalt-silicon alloys of Example 7; Fig. 18 is a graph showing the effect of the stoichiometric ratio on electrical conductivity in the copper-nickel-chromium-cobalt-silicon alloys of Example 7; Fig. 19 is a flow chart of the treatment of the alloys in Example 8; Fig. 20 is a graph showing the effect of the stoichiometric ratio in IACS% on the alloys of Example 8 processed by the SA-CR-aging-CR-age aging process, of 475 ° C / 300 ° C .

Fig. 21 is a graph showing the effect of the stoichiometric ratio on the strain resistance in the alloys of Example 8 processed by the SA-CR-aging-CR-aging with ages of 475 ° C / 300 ° C; Fig. 22 is a flow chart of the treatment of the alloys in Example 9; Fig. 23 is a schematic diagram of a tapered edge hot rolling specimen; Fig. 24 is a photograph of hot rolled K224 (without Cr), showing large edge cracks; Fig. 25 is a photograph of the hot rolled K225 (0.11 Cr), which shows no edge cracks; Fig. 26A is a photograph of the results of the tool wear test of the alloy without Cr RN033407; Y Fig. 26B is a photograph of the result of the • tool wear test of the alloy containing Cr RN834062; Fig. 27 is a flow chart of the treatment of the alloys in Example 10; Fig. 28 is a graph showing the effect of the stoichiometric ratio in% of IACS in the alloys of Example 8 and Example 10 (Cr and n low) processed by the SA-CR-aging-CR-aging process with ages of 475 ° C / 300 ° C; Y Fig. 29 is a graph showing the effect of the stoichiometric ratio on the strain resistance in the alloys of Example 8 and Example 10 (with low Cr and Mn) processed by the SA-CR-aging process-CR- aging with aging of 475 ° C / 300 ° C; Fig. 30 is a flow graph of the treatment of the alloys in Example 11; Y Fig. 31 is a flow chart of the treatment of the alloys in Example 12; Fig. 32 is a flow chart of the treatment of the alloys in Example 13; Fig. 33 is a flow chart of the treatment of the alloys in Example 14; Fig. 34 is a flow chart of the treatment of the alloys in Example 15; Fig. 35 is a flow chart of the treatment of the alloys in Example 16; Fig. 36 is a plot of the V block of 90 ° - MBFi / t BW against the deformation resistance for the alloys and processes of Examples 13, 14, 15, and 16; Y Fig. 37 is a graph of% IACS versus strain resistance for the alloys and process of Examples 13, 14, 15, and 16.

DETAILED DESCRIPTION There is a need in the market for copper strip alloys with higher strength and electrical conductivity, together with good stress relieving resistance. · These combinations of properties are particularly important for parts that are formed in various electrical interconnections for use in connector applications and multimedia electrical terminals. The alloys Commercial copper * nté available, such as C510 (phosphor-bronze), C7025, C7035,, C17410 and C17460 are being used in these applications for their generally favorable combinations of strength and conductivity. However, while these alloys have adequate strength for most current-carrying applications, the constant trend for miniaturization of components demands copper alloys that offer high strength in reasonably good electrical conductivity and reasonably good tensile resistance combination. good together with cost. reasonable. It is also desirable to minimize and eliminate potentially toxic alloying elements such as beryllium.

The alloys that are used for multimedia interconnections require high resistance to avoid damage during insertion of the connector and to maintain good contact force while in service. For these applications, good but not especially high electrical conductivity is all that is required, since the conductivity merely needs to be sufficient to carry a signal current, and it does not need to be the high levels necessary to avoid excessive I2R heating in applications of higher energy. For these applications, there are still more stringent requirements for mechanical stability at ambient service temperatures and slightly elevated, as characterized by good resistance 'of stress relaxation a. approximately 100 ° C, for example.

The alloy compositions of the preferred embodiments of this invention and the scheme used to process the finishing toughenedings surprisingly provide a highly desirable combination of properties to meet the needs of both automotive and multimedia applications, particularly high strength together with moderately conductivity. high. In particular, the alloys of the preferred embodiments of the present invention are capable of being processed into strip products with combinations of deformation resistance / electrical conductivity of at least about 137 ksi with a conductivity of at least about 38% of IACS, more preferably a strain resistance of at least about 143 ksi, with a conductivity of at least about 37% IACS, and much more • preferably a strain resistance of about 157 ksi, with a conductivity of at least less approximately 32% of IACS.

The alloys of the preferred embodiment of the present invention have an improved combination of strain resistance and electrical conductivity, good stress relieving resistance, together with. levels modest bending capacities, consist essentially of about 1.0 to about 6.0 weight percent nickel, from about 0.5 to about 2.0. percent by weight of silicon, from 0.0 to about 3.0 weight percent cobalt, from about 0.01 to about 0.5 weight percent magnesium, from 0.0 to about 1.0 weight percent chromium, and from 0.0 to about 1.0 weight percent. one hundred weight in each of: tin and manganese, the rest of the alloy which is copper and impurities. More preferably, the alloy consists essentially of about 3.0 to about 5.0 weight percent nickel, about 0.7 and about 1.5 weight percent silicon, 0.0 to about 2.0 weight percent cobalt ,. from about 0.03 to about 0.25 weight percent magnesium, from about 0.0 to about 0.6 weight percent chromium, and from 0.0 to 1.0 weight percent each of tin and manganese, the remainder being copper and impurities. Where an optimum level of strain resistance and electrical conductivity is necessary, for example a combination of YS 140 ksi / 30% IACS, the most preferred alloy ranges from about 3.5 to about 3.9 weight percent nickel; from about 1.0 to about 1.2 weight percent silicon; from about 0.8 to about 1.0 per weight percent cobalt, from about 0.05 to about 0.15 weight percent magnesium, from 0 to about 0.1 weight percent chromium, and from 0.0 to about 1.0 weight percent each of tin and manganese, the rest that is copper and impurities. Generally, excessive coarse second phases are present when the alloying elements are substantially beyond the indicated upper limits.

The electrical conductivity and the deformation resistance of the alloy are higher when the ratio (Ni + Co) / (Si-Cr / 5) is controlled between about 3 and about 7, and more preferably between about 3.5 and about 5. The Ni / Co ratio is optimal for deformation resistance and conductivity when controlled between approximately 3 and approximately 5.

Magnesium generally increases the tensile strength of the stress and the softening resistance in the finished products; It also increases the softening resistance during the annealing heat treatments of aging in process. When present at low levels, the Sn generally provides solid solution strength and also increases the softening resistance during annealing heat treatments of aging in process, 1 without excessively damaging conductivity. Low Mn levels generally improve bending formability, although with a loss of conductivity.

The preferred embodiment of the process of the present invention comprises casting and casting; hot rolling (preferably 750 ° to 1050 ° C), optional grinding to remove the oxide, and optional homogenization or intermediate bell annealing, cold rolling to a suitable size for solution formation, solution annealing treatment ( preferably at 800 ° -1050 ° C for 10 seconds to one hour) followed by a rapid quenching or cooling to room temperature to obtain an electrical conductivity of less than about 20% IACS /-(ll.6 MS / m) and a Equidimentional grain size of approximately 5 - 20 μp ?; a reduction of cold rolling from 0 to 75% in thickness; an aging hardening anneal (preferably at 300-600 ° C from 10 minutes to 10 hours); and optionally a reduction from 10 to 75% of additional cold rolling in thickness to a finishing gauge; and a second aging hardening anneal (preferably 250 to 500 ° C for 10 minutes to 10 hours). The resulting alloy can also be processed to a finishing gauge without using a heat treatment solution in process formation by using lower temperature bell annealing treatment cycles. with work in cold and intermediate. In addition, one or more optional recrystallization alloy (s) may be added to the process during reduction of the hot rolled gauge to the proper thickness for solution formation.

The preferred scheme results in the alloy having a deformation strength of at least about 140 ksi, and a conductivity of at least about 30% of "IACS, the conductivity involves the formation of solution at about 900 ° to 1000 ° C. , lamination cooled by approximately 25%, aging at approximately 450 ° - 500 ° C for 3 - 9 hours, cold rolling by approximately 20 - 25% at finishing gauge, and aging 300 ° - 350 ° C for 3 - 9 hours .

While this description is particularly set forth in a process for the manufacture of a copper alloy strip, the alloys of the invention and the processes of the invention are equally susceptible to the manufacture of other copper alloy products, such as sheets. thin, wire, bar and tube. In addition, processes other than conventional casting, such as strip casting, powder metallurgy and spray casting are also within the scope of the invention.

The alloys and methods of the preferred embodiments will be understood to be improved from the following illustrative examples: Example 1 - Increase of Alloy Levels Increase Resistance; Cobalt Substitution Improves Both Resistance and Conductivity A series of ten free laboratory ingots with the compositions listed in Table 2 were melted in a silica crucible and emptied in Durville form in steel molds, which after the tapping were approximately 4"X4" X 1.75". Fig. 1 is a flow chart of the process of this Example 1. After soaking for two hours at 900 ° C they were hot rolled in three steps at 1.1"(1.6" / 1.35"/ 1.1"), reheated to 900 ° C for 10 minutes, and hot rolled additionally in three steps at 0.50"(0.9" / 0.7"/ 0.5"), followed by rapid cooling with water, followed by an over-aging homogenization or annealing at 590 ° for 6 hours. After they were cut and ground to remove the surface oxide, the alloys were cold rolled to 0.012"and treated with heat in solution in a fluidized bed furnace during the time and temperature listed in Table 2. The time and temperature were selected. the temperature to achieve an approximately constant grain size.The alloys were then subjected to an aging anneal of 400 ° to 500 ° C for 3 hours, designed to implement the strength and conductivity.The alloys were then cold-rolled to 25% to 0.009"and they got old from 300 ° to 400 ° C for 4 hours. The properties measured after the second annealing of aging are presented in Table 3. The data indicate that the deformation resistance increases with the increase of the alloy levels in the ternary alloys J994 to J999, from 127 to 141 ksi of resistance of performance when Si levels vary from 0.8 to 1.3%, respectively. Comparing J994, K001 and K002 to examine the effect of Co on alloys about 0.8% Si, the substitution of Co for Ni increases both the deformation resistance and the conductivity. Considering a substitution of Co for Ni in the alloys with ~ 1.2% Si, K003 shows a decrease in the deformation resistance and an increase in the conductivity, while K004 shows an increase in the deformation resistance and decrease in the conductivity when compared to J998.

Having a Ni / Co ratio of approximately 3 (K002 and K004) leads to a higher resistance than a Ni / Co ratio of 1 (K001 and K003), particularly at the higher Si level. The alloys of n K011 and K012 show evidence that the substitution of Mn for Ni improves the strength / bending properties, but at a significant loss of conductivity. Sn appears to provide strength in solid solution, when compared to J994 to K036 and K037.

Table 2 - Alloys of Examples 1 and 2 Alloy Composition analyzed,% by weight Solution annealing conditions Grain size um J994 Cu -3.33 NI -0.81 SI 850 * 0-1 minute 11.2 J995 Cu- 3.78 Ni -0.92 Si 900 ° C-1 minute 165 J & 6 Cu-4-.17Ni-1.03S1 00 ° C-1 minute 22.1 J997 Cu-4.48 i-1.12Sl 900 ° C-1 minute 22.1 J99 & Cu -4.86 M-1.24 Yes 900"C-1 minute 12.9 J999 Cu -5.39 Ni -1.35 SI gOCC -2 minutes 14.1 K001 Cu -1.65 Ni -0.82 Si-1.65 Co 1000 ° C-30 seconds 12.9 K002 Cu -2.56 Ni -0.80 Si- 0.79 Co 950eC-1 minute 17.7 003 Cu -2.45 Ni -1.23 Si- 2.48 Co 10O0 ° C- 30 seconds 6.7; K004 Cu-3.70Nl-1.22SI-1.15Co. 1000'C- 30 seconds 12.9 K009 Cu -1.74 Ni -0.78 Yes - 1.67 Mn 850 ° C-30 seconds 28.2 K010 Cu -2.65 Ni -0.79 Yes -0.79 Mn 850eC-30 seconds 22.1 K011 Cu -251 Ni -1.19 Yes -2.56 Mn 850 * C - 1 minute 9.1 012 Cu -3.70 Ni -1.21 Si- 1.19 Mn 850 * C- 1 minute, 9.8. 013 Cu -3.22 NI -0.81 Yes- 0.10 Cr 850PC- 1 minute 12.6 014 Cu -3.31 Ni -0.82 Si- 0.18 Cr 850 ° C-1 minute 10.7 KOI 5 Cu -4.82 Ni -1.21 Yes -0.09 Cr 900"C-1 minute 15.5, K015 Cu -4.89 Ni -1.26 Si- 0.18 Cr 900 ° C-1 minute 12.9 KD35 Cu -3.69 Ni -0.73 Si- 0.52 Sn 850 ° C-2 minutes 10.3 K037 Cu- 3.66 Ni -0.77 Si- 0.93 Sn 850 ° C-2 minutes 16.2 K00 Cu - 3.74 NI - 0.72 Si - 0.08 Mg 850 ° C - 2 minutes 17.7 K041 Cu -3.78 Ni -0.76 Yes -0205 MB 850"C-2 minutes 18.6 Table 3 Properties of the Alloys of Examples 1 of the SA-aging-CR-aging process Aging Alloy% of IACS YSTS / S 90 ° MBR / t ksl / ksl /% J994 450/300 36.8 126.7 / 130.8 / 2 2.9 / 3.4 J995 450/300 35.5 130.8 / 134.7 / 1 3.2 / 5.7 J996 450/300 34.5 132.7 / 138.572 3.1 / 6.9 J997 450/300 33.7 135.3 / 139.3 / 2 3.7 / 6.7 J998 450/300 34.3 137.9 / 144.2 / 2 3.3 / 8.6 J999 450/300 34.2 140.9 / 147,1 / 2 3.4 / 6.7 K001 500/300 40.3 1295 / 134.42 002 500/350 40.5 130.3 / 135,82 3,852 K003 450/300 37.8 129.7 / 134.32 3.5 / 3.7 K004 450/300 28.4 45.3 / 150.B / 2 5.1 / 6.8.

K009 450/350 16.5 108.1 / 113.34 - ' K010 450/300 22.9 127.1 / 131.3 / 2 - K011 400/300 11.9 137.6 / 141.0 / 2 2.43.2 K012 400/300 i 17.0 135.4 / 140.4 / 2 2.4 / 3.7 K013 450/300 36.7 125.4 / 129.6 / 2 - K014 450/300 36.2 128.0 / 131.9 / 2 - ·, K015 450300 33.8 135.6139.8 / 2 3.55.2 K016 450/300 32.4 136.0 / 140.4 / 2 3.3 / 5.2 K036 450/300 34.3 131.5 / 143.1 / 1 3.9 / 6.9 K037 45Q / 300 30.8 135.2 / 147.1 / 2 3.5 / 6.8 K040 450/350 38.4 125.4136.5 / 2 |- K041 450j¾50 37.7 123.7 / 135.5 / 1 Example 2 - Cobalt Improves Resistance The selected alloys of Example 1 were heat treated in solution in a fluidized bed furnace for the time and temperature listed in Table 2. Fig. 2 is a flow chart of the process of this Example 2. Subsequently the alloys were laminated cold 25% to 0.009"then subjected to an aging anneal of 400 ° C at 500 ° C for 3 hours, after an additional cold reduction1 of 22% at 0.007", the samples were annealed by aging at temperatures of 300 ° to 400 ° C for 3 hours. The properties of the representative conditions are listed in Table 4. The fold properties in many cases are somewhat better in strength similar to the process in Example 1. The additions of Co (K003 and K004) and Sn (K037) provide the highest strength increase of the alloys in this example.

Table 4 Properties of the Alloys of Examples 2 of the SA-CR-aging-CR-aging process Aging Alloy% of IACS Y & TS / EI 90s BRA keVksl /% J994 450/300 38.3 130.0 / 13 SU 2.3 / 3.7 J997 460/300 37.7 125.2 / 132.7 / 2 2.9 / 8.9 J998 400300 26.8 128.4 134.0 / 2 3.1 / 4.0 J999 400/300 29.5 131.9 / 135.4 / 2 3.1 / 5.1 K002 450 300 35.1 125.0 129.2 / 1 2.44.9 K003 450/300 33.7 135.2 / 140.3 / 2 3.1 / 4.0 K004 450 300 31.9 134.4 / 139.7 / 2 3.7 B.7 K014 460/300 38.1 127.9 / 132.3 / 2 2.3 / 4.0 · K036 450/300 36.0 129.2 / 131.8 / 1 3.1 / 3.9 K037 450/300 32.0 135.2 / 139.8 / 2 3.3 / 4.7 K040 450/300 38.7 127.1 / 129.3 / 1 - K041 450/300 38.4 132.4 / 136.4 / 1, 3.S / 4.7 Example 3 - Cobalt and Chromium Levels and Relation (Ni + Co) / (Si-Cr / 5) A series of ten-pound laboratory ingots with the compositions listed in Table 5 were melted in a silica crucible and emptied in Durville form in steel molds, which after the mazarotajé were approximately 4"X 4" X 1.75" Figure 3 is a flow chart of the process of this Example 3. After soaking for two hours at 900 ° C they were hot rolled in three steps at 1.1"(1.6" / 1.35"/ 1.1"), reheated to 900 ° C for 10 minutes, and hot rolled further in three steps at 0.50"(0.9" / 0.7"/ 0.5"), followed by rapid cooling with water.The cooled plates were then soaked at 590 ° C for 6 minutes. hours, they were cut and then ground to remove the surface oxides developed during hot rolling: The alloys were then cold rolled to 0.012"and treated with heat in solution in a fluidized bed furnace for 60 seconds at temperatures listed in Table 5 The temperature was selected to maintain a fairly constant grain size. The alloys were then annealed for aging at 400 ° C to 500 ° C for 3 hours, designed to increase strength and conductivity. The alloys were then cold rolled at 25% to 0.009"and aged 300 °. at 400 ° C for 4 hours. measurements after the second annealing by aging are shown in Table 6. From this data set, it can be seen that the additions to a Cu-Ni-Si base alloy of Co (K068), Cr (K072), or Both Co and Cr (K070) achieve the best combinations of strength, conductivity and bending formability. It is also observed that the relatively high Si levels of 1.2% and above were present in the samples with the highest resistance. While there was some evidence of Sn resistance, this was accompanied by poor bending formability. In Table 5, it can be seen that the ratio (Ni + Co) / (Si-Cr / 5) is very close to 4 for most alloys, particularly K068, K070 and K072. Also, the Ni / Co ratio was close to 3 for K068 and K070. The deformation resistance is plotted against the conductivity in Figure 4, and against the fold 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 Composition analyzed,% by weight Ratio NÍ / Co Annealing Temperature Size of (N¡ + Co) / (S¡-Cr / 5) in Grain Solution um K056 Cu - 4.94 Ni - 0.97 Si - 0.86 Sn 5.09 900 ° C 15 Cu - 2.63 Ni - 0.73 Co - 0.80 S - 18 925 ° C 057 0.8B Sn 4.20 3.60 Cu - 3.80 Ni - 0.97 Co - 1.24 Si - 14 950 * C K058 0.83 Sn 3.85 3.92 K059 Cu - 3.27 NI - 0.82 Yes - 0.22 Mn 3.99 850 * C 20 Cu - 3.83 Ni| 1.28 Co - 1.27 Si - 8 950'C K061 0.31 Mn 4.02 2.99 K065 Cu - 4.96 Ni - 1.25 SI - O.0B5 fl 3.97 900'C 17 Cu - 3.29 Ni - 0.84 Si - 0.33 Mn- 10 850 * C K066 0.092 Mg 3.92 Table 6 Properties of the SA-aging-CR-aging process of Example 3 Example 4 - Cobalt and Chromium for Resistance and Formability The alloys of Example 3 were heat treated in solution in a fluidized bed furnace for 60 minutes. 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 at 5% to 0.009"then subjected to annealing by aging of 400 ° to 500 ° C for 3 hours After an additional cold reduction of 22% at 0.007", the samples were annealed by aging at temperatures of 300 ° to 400 ° C for 3 hours. The properties of the representative conditions are listed in Table 7. Similar to Example 3, of particular note are the alloys K068, K070 and K072, which show that the alloys containing Co, Cr or a combination of both achieve the resistance levels Taller. Bending formability data indicate that K068 and K070 which both contain Co have the best formability at higher strength. The deformation resistance is plotted against the conductivity in Figure 7, and against the bending formability in Figure 8. The values for the alloys K068, K070 and K072 are observed.

Table 7 Properties of the SA-CR-aging process-CR-aging of the Exhibition Alloys 4 Aging Alloy% of IACS YS / rs / B 90 * MBR / t ksl / ksl /% K056 450/300 29.1 147.4 / 152.4 / 2 5.7 / 8.6 K057 450/300 29.7 136.1 / 141.9 / 2 2.0 / 5.7 K058 450/300 25.8 146.7 / 153.3 / 1 2.08.6 K065 450/300 34.7 142.9 / 145.42 3.6 / 4.9 K067 500/300 38.4 137.4 / 141.7 / 3 2.9 / 5.7 K06B 450/300 30.3 151.6 / 155.31 '3.6 / 4.9 K069 450/300 29.7 139.4 145.7 / 1 2.9 / ?. ß K070 450/300 31.1 152.3 / 157.9 / 2 2.9 / 3.9 K071 450/300 34.8 143.8 / 1 7.6 / 2 2.9 / 3.9 K072 450/300 31.4 155.4 / 161.31 / 1 2.7 / 8.6 K073 450/300 34.7 147.2 / 150.8 / 2 2.7 / 3.9 K074 450/300 29.8 153.9 / 160.0 / 1 2.1 3.9 075 450/300 26.5 151.4 / 158.2 / 2 2.0 / 11.0 K076 450/300 28.1 142.8 / 149.0 / 1 2.1 / 8.6 Example 5 - Ratio of Nickel: Cobalt A series of ten-pound laboratory ingots with the compositions listed in Table 8 melted in a silica crucible were emptied in Durville form into steel molds, which after the tapping were approximately 4"X 4" X 1.75" Figure 9 is a flow chart of the process of this Example 5. This group of alloys is based on K068, K070 and K072 of Table 5, where the complete alloy level and the Ni / Co ratio were varied while maintain the stoichiometric ratio ((Ni + Co) / (Si-Cr / 5)) close to 4.2 After soaking for two hours at 900 ° C they were hot rolled in three steps at 1.1"(1.6" / 1.35"/ 1.1"), were reheated at 900 ° C for 10 minutes, and hot rolled further in three steps at 0.50" (0.9"/ 0.7" / 0.5"), followed by rapid cooling with water. soaked at 590 ° C for 6 hours, cut and then ground to remove surface oxides developed during hot rolling. The alloys were then cold rolled to 0.012"and heat treated in solution in a fluidized bed furnace for 60 seconds at the temperature listed in Table 8. temperature was selected to maintain a fairly constant grain size. The alloys were then annealed for aging at 450 ° to 500 ° C for 3 hours, designed to increase strength and conductivity. The alloys were then cold rolled from 25% to 0.009"and aged from 300 to 400 ° C for 4 hours: The properties measured after the second annealing by aging for the process with a first aging of 475 ° C and a second Aging of 300 ° C are shown in Table 9. For the set of only Co of the compositions (K077 to K085), the values of strain resistance tend to increase with the content of i highest alloy. For example, K078, with a 'Ni + Co + Cr + Si value of f 6.24, had a strain resistance of 155 ksi while K084 with a Ni + Co + Cr + Si value of 5.22 had a strain resistance of 139 ksi. A Ni / Co ratio of 3 to 4 provides better resistance than a ratio of 5, when comparing K077 (ratio Ni / Co of 3.62) and K078 (ratio of Ni / Co of 3.83) to K079 (ratio of Ni / Co to 5.04), as well as also the comparison of K080 (ratio of Ni / Co of 3.32) and K081 (Ni / Co ratio of 3.93) to K082 (Ni / Co ratio of 4.89). The graphs of the deformation resistance vs Ni / Co ratio in Figure 10 illustrate this, with the exception of K085, which has a Si level higher than K083 and K084. The alloys that contain Co-and-Cr-, K086 to K094, were not as sensitive to the total alloy levels and the Ni / Co ratio as the alloys only of Co. The alloys only of Cr (K095 to K097) also had comparable properties with the other types of alloy. - Table 9 Properties of the SA-aging-CR-aging process of Example 5 Aging Alloy% of IACS YS / TS EÍ 90 ° BFVt kst / ksl /% K077 475/300 29.1 152.1 / 159 ^ 4 5.2 / 5.2 K078 475/300 29.7 155.5 / 1 B2.34 52 / 5.2 K079 475/300 30.7 143.7 / 160.1 / 4 K080 475/300 31.2 142.4 / 147.9 / 3 K0B1 475300 30.7 144.2 / 148.33 4.0 / 6.1 K082 475/300 32.2 137.7 / 142.7 / 2 K083 475/300 31.1 140.0 / 145.8 / 3 d.2 / 5.2 KÜ84 475/300 32.1 138.9 / 145.6 / 3 085 475/300 31.8 140.4 / 146.3 / 2 088 475/300 30.1 151.6 / 157.8 / 4 5.2 / 6.1 K087 475300 30.5 149.4 153.6 / 3 5.2 / 3.6 ??H.H? 475/30 30.4 152.2 / 159.3 / 4 5.2 / 5.2: 089 475Q00 30.3 149.0 / 155.6 / 3 4.0 / 5.2. ? 090 475/300 313 151.9 / 157.4 / 3 5.2 / 3.8 ? 091 475/300 30.7 149.5 / 154.5 / 3 5.2 6.1; ? 092 475/300 30.8 146.5 / 152.1 / 3 4.0 / 5.2 083 475/300 30.3 147.2 / 153.4 / 4 5.2 / 5.2 ? 094 475/300 31.2 143.1 / 154.4 / 2 4.0 / 3.8; ? 095 475/300 30.7 150.2 / 159.1 / 3 3.8 / 6.1 ? 096 475/300 32.1 153.3 / 160.6 / 4; 4.0 / 6.1 ? 097 475/300 31.9 148.7 / 155.53 as / 5.2 The alloys of Table 8 were treated with heat in solution in a fluidized bed furnace 60 seconds at the temperature listed in Table 8. Subsequently 'the alloys were cold rolled from 25% to 0.009' then subjected to annealing by aging at 450 to 500 ° C for 3 hours After an additional cold reduction of 22% at 0.007", the samples were annealed by aging at temperatures of 300 to 400 ° C for 3 hours. The properties of the samples gave the first and second ages at 450 ° C and 300 ° C, respectively, are listed in Table 10. Co-only alloys showed a sensitivity to the complete alloy levels with this scheme that was not found in alloys containing Cr. Alloys of only Co in the 150 ksi and above deformation resistance were K077 and K078, while all alloys containing Cr reached or approached that level of resistance. The strength-bending properties for this process are quite similar to those in Table 9.

Example 6 - Ratio of Nickel: Cobalt Laboratory ingots with the compositions listed in Table 11 were melted in a graphite crucible and emptied in Tamman form into steel molds, which after the nibbling were 4.33"X 2.17" X1.02. "Figure 11 is a Flow chart of the process of this Example 6. For an objective content of 1% and a Cr content of 0.5%, one alloy is the one containing Co and the other is free of Co, the content of Ni is adjusted in order to maintain a stoichiometric ratio ((Ni + Co) / (S'i-Cr / 5)) of close to 4.2 After soaking for two hours at 900 ° C they were cold rolled to 0.472", whereby they were reheated then at each step at 900 ° C for 10 minutes. After the last step the bar was cooled with water. After trimming and grinding to 0.394"in order to remove the surface oxide, the alloys were cold rolled to 0.0106" and heat treated in solution in a fluidized bed furnace for the time and temperature listed in Table 11. The time and temperature were selected to achieve grain sizes below 20 μp ?. The alloys were then annealed for aging at 450 to 500 ° C for 3 hours, designed to increase strength and conductivity. The alloys were then cold rolled from 25% to 0.0079"and aged 300 or 400 ° C for 3 hours.The properties measured after the second annealing by aging are presented in Table 12. The formability was measured via the V-shaped block. The data indicate that both alloys are capable of achieving a strain resistance of 135 ksi, still the BS variant that contains Co shows a better softening resistance that can be observed with the increase of the. Annealing temperature by aging The slightly better bending capacity of the BS variant is presumably due to the slightly lower grain size after annealing in solution.

Table 11 Alloys of Examples 6,% by weight Alea- Ni Co Cr Si Mg Relationship * Ni / Co Conditions SA Size Ni + Co) / (Si- of Cr / 5) grain, um BR 3.59 0.48 1.00 3.97 915 ° C-1 minute 10-15 BS 3.18 0.47 0.49 0.97 4.19 6.77 950 ° C-1 minute 5. Í0 TABLE 12 Process Properties SA-endemic-aging-eclmlent CR-en 6 Example 7 - Relation (Ni + Co) / (Si-Cr / 5) A group of alloys was emptied and processed using once again the basic compositions of K068 (Co only), K070 (Co and Cr) and K072 (Cr only) of Table 5 as a base, but in this case with a drop gradual 'in Si levels, thereby increasing the stoichiometric (Ni + Co) / (Si-Cr / 5) ratio above the 3.6 to 4.2 range of the previous alloys. The Ni and Co levels were designed to be constant for each of the three types of alloys. A series of ten-pound laboratory ingots with the compositions listed in Table 11 were melted in a silica crucible and emptied in Durville form into steel molds, which after grinding were approximately 4"X 4" X 1.75. "; The K143 to K146 are variants of K072, K160 to K163 are variants of K070, and K164 to K167 are variants of K068. Figure 12 is a flow chart of the process of this Example 1. After soaking for two hours at 900 ° C they were hot rolled in three steps at 1.1"(1.6" / 1.35"/ 1.1"), they were reheated to 900 ° C for 10 minutes, and were further hot rolled in three steps at 0.50"(0.9" / 0.7"/ 0.5"), followed by cooling with water. The cooled plates were then soaked at 590 ° C for 6 hours, trimmed and then ground to remove the surface oxides developed during hot rolling.; The alloys were then cold-rolled to 0.012"and treated in heat with solution 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. then they were cold rolled from 25% to 0.009"and aged at 450, 475 and 500 ° C for 3 hours. The properties of each aging temperature for the alloys of the current example, as well as K068, K070, K072, K078, K087 and K089 are listed in Table 14. For each type of alloy, the deformation resistance decreases according to the stoichiometric ratio it increases above about 4.5, and drops below 120 ksi in a ratio of about 5.5. This is shown in Figures 13 to 15 for Cr alloys (plus data from K072), Co alloys (plus data from K068 and K078), and Co-Cr alloys (plus data from K070, K087 and K089), respectively. In the alloys of Co and Cr, the conductivity decreases as the stoichiometric ratio increases above about 4.5, while for alloys with both Co and Cr there is no clear relationship between stoichiometry and conductivity. This is shown graphically in Figures 16 through 18. Based on these data it is evident that the best deformation-conductivity resistance properties occur when the stoichiometric ratio is maintained between 3.5 and 5.0.

Table 14 Properties after annealing in solution, 25% cold rolling and aging of Example 7 Example 8 - Relation (Ni + Co) / (Si-Cr / 5) A series of laboratory ingots of ten: pounds with the compositions listed in Table 15 melted in a silica crucible and emptied in Durville form in steel molds, which after the lining were approximately 4"X 4" X 1.75 Figure 19 is a flow chart of the process of this Example 8. After soaking for two hours at 900 ° C they were hot rolled in three steps at 1.1"(1.6" / 1.35"/ 1.1"), reheated at 900 ° C for 10 minutes, and hot rolled additionally in three steps at 0.50"(0.9" /. 0.7"/ 0.5"), followed by cooling with water.The cooled plates were then soaked at 590 ° C during 6 hours, they were cut and then ground to remove the surface oxides developed during the hot rolling.

The alloys were then cold-rolled to 0.012"and treated with heat in solution in a fluidized bed furnace for 60 seconds at 950 ° C. The grain size varied from 6 to 12 μp.

: The alloys were then subjected to an annealing 'by i, 5 aging of 450 or 475 ° C for 3 hours, they were designed to increase the resistance and conductivity. The alloys were then cold-rolled from 25% to 0.009"and (j) aged at 300 ° C for 4 hours.

|: After the second annealing due to aging '10 represent in Table 16. j Table 17 has properties measured after ': that the samples were heat treated in solution in a ; fluidized bed furnace for 60 seconds at 950 ° C, ! cold rolled from 25% to 0.009", gave an annealing of ! '15 aging at 475 ° C for 3 hours, rolled in cold ,: from 22% to 0.007", and gave a final annealing of 300 ° C • j for 3 hours. The results show the viability of a , i · \: range of compositions with Si from 1.0 to 1.2%, with a 'í ! Nt / Co ratio of 4, and a stoichiometric ratio 1 , | 20 (((Ni + Co) / (Si-Cr / 5))) from 3.5 to 5.0. This is shown !: · Graphically in Figures 20 and 21, which graph the j, conductivity data and strain resistance of the Table 17 against the stoichiometric ratio. These graphs show the deformation strengths of 140 ksi or more i; 25 additions combined with 25% conductivity of IACS or more highs that are obtained for this process when the ratio is between 3.0 and 5.0. It was not discovered that Cr affects the significant properties in the alloys of this example.

Tension relaxation tests were run on samples of K188 and K205 that were cold-rolled to 0.012"of the ground-cold-rolled plate, annealed in solution at 950 ° C for 60 seconds, cold-rolled 25% at 0.009", and annealed at 475 ° C for 3 hours. The stress relaxation tests were run at 150 ° C for 3000 hours in the longitudinal and transverse orientation samples. The results in Table 18 show that both alloys had excellent stress relaxation resistance, over 85% of tension that remains after 1000 hours at 150 ° C, without considering the Cr content or the orientation of the sample.

Table 15 Alloys of Example 8 Alloy Composition analyzed,% by weight Ni / Co estequlomethylca of um K183 Cu - 3.40 Ni - 0.81 Co- 1.16 Si - 0.42 Cr- 0.019 Mg 4.20 3.91 7.3 K189 Cu - 3.20 Ni - 0.72 Co - 1.05 SI - 0.38 Cr - 0.033 Mg 4.46 4.02 10.1 1T0 Cu - 322 Ni - 0.70 Co - 1.28 Si - 0.31 Cr - 0.036 Mg 459 322 Ev5 K191 Cu - 3.22 Ni - 0.70 Co- 1.05 Si - 0.53 Cr- 0.064 Ma 4.58 4.16 9.5 K192 Cu- 2.94 Ni - 0.69 Co- 1.29 Si - 0.55 Cr- 0.062 Mg 4.24 3.08 10.9 K193 Cu - 3 ^ 1 Ni - 0.80 Co- 1.05 Si - 0.34Cr- 0.117 Mg 3.56 4.18 8.6 K194 Cu - 3.20 Ni - 0.84 Co - 1.30 SI - 0.22 Cr- 0.035 Mg 3.80 3.22 7.8 K195 Cu - 3.18 Ni - 0.86 Co -0.81 Si - 0? 2 Cr- 0.070 Mg 3.71 5.72 7.1 196 Cu - 3.19 NI- 0.89 Co - 1.28 SI - 0 ^ 7 Cr-0.111 Mg 3.60 3.49 7.7 K197 Cu - 3.61 Ni - 0.70 Co - .08 Si - 0.38 Cr - 0.067 Mg 5.14 4.36 10.7 K198 Cu - 3.60 NI - 0.70 Co - .28 SI - 0.39 Cr - 0.077 Mg 5.13 3.58 8.7 K199 Cu - 3.60 Ni - 0.70 Co - 1.0B Si - 0.60 Cr- 0.076 Mg 5.13 4.5B 9.3 K200 Cu - 3.60 Ni - 0.70 Co - .28 SI - 0.60 Cr - 0.092 Mg 5.14 3.70 9.3 K201 Cu - 3.63 Ni - 0.88 Co - 1.04 Si - 0.29 Cr - 0.065 Mg 4.12 4.59 6.0 K202 Cu - 3.62 1 ^ - 0.90 Co - 1.27 Yes - 0.36 Cr -0.101 Mg 4.04 3.77 7.4 K203 Cu - 3.59 Ni - 0.89 Co - 1.05 SI - 0.56 Cf - 0.076 Mg 4.04 4.77 8.1 K204 Cu - 3.58 Ni - 0.88 Co - 1.27 Si - 0.56 Cl - 0.075 Mg 4.09 3.85 5.9 K205 Cu - 3.73 Ni - 0.91 Co- 1.13 Yes - 0.082 Mp 4.09 4.11 12.1 K206 Cu - 3.53 i - 0.81 Co - 1.02 Si - 0.080 Mg 4.38 4.25 12.2 207 Cu - 3.53 Ni - 0.78 Co - 1.25 SI - 0.055 Mg 4.55 3.44 9.9 203 Cu- 3.57 i - 1.00 Co - 1.02 Si - 0.070 Mg 3.57 4.48 7.6 K209 Cu - 3.54 Ni - 1.02 Co- 1.25 Si -0.O85 Mg 3.47 3.65; .

K210 Cu- 3.94 NI - 0.B2 Co - 1.06 SI - 0.149 Mg 4.78 4.49 9.5 K211 Cu - 3.97 NI - 0.80 Co- .24 SI - 0.065 Mg 4.97 3.85 11.5 212 Cu - 3.95 i- 0.99 Co - 1.04 Si - 0.100 Mg 4.01 4.75 10.2 213 Cu - 3.97 NI - 0.99 Co - 22 Si - 0.079 Mg 4.01 4.07 10-2.

Table 16 Properties of the SA-aging-CR-aging Process of Example 8 Alloy Aging% of IACS YS / rs / a 90 ° MBFVt ksi / ksi /% K188 450/300 29.3 149.5 / 156.1 / 2 3.3 / 5.2 K189 475/300 33.6 147.3 / 153.8 / 2 4.0 / 4.0 · K204 450/300 29.7 149.6 / 155.1 2 '4.0 / 5.2 K205 475/300 34.2 149.8 / 155.7 / 2 4.0 / 5.2 K208 475/300 35.0 147.9 / 153.9 / 2 4.0 / 5-3 K213 475/300 34.E 150.8 / 157.4 / 2 5.2 / 55 Table 18 Stress Relaxation Data at 150 ° C for cold rolled samples of 25% and aged at 475 ° C for 3 hours of Example 8 Example 9 - Effect of Cr A series of ten-pound laboratory ingots with the compositions listed in Table 19 were melted in a silica crucible and emptied in Durville form into steel molds, which after tapping were approximately 4"X 4" X 1.75. Figure 22 is a flow chart of the process of this Example 9. The ingots were then machined to have tapered edges, as schematically illustrated in Figure 23, to create a higher state of edge tension stress. This condition is more prone to edge cracking than standard flat edges, and thus more sensitive to alloy additions, in this case Cr. The alloys are soaked for two hours at 900 ° C, and are laminated at two steps at 1.12". (1.4"/ 1.12") then cooled with water. After an examination for cracks, the bars were reheated to 900 ° C. for two hours and rolled in three steps at 0.50"(0.9" / 0.7"/ 0.5"), followed by cooling with water. It was discovered that without Cr, K224 developed large cracks during the first few steps of hot rolling, which were During the remaining 'steps', none of the Cr-containing alloys developed large cracks during hot rolling.Some of the alloys showed small cracks after the initial steps which are believed to be due to defects in casting, but these they were not enlarged during the subsequent steps The Cr effect was the same independent of the Cr level, from 0.11% to 0.55% Examples of edge conditions of K224 and K225 after hot rolling are shown in Figures 24 and 25. The addition of a small amount of Cr 'would reduce the cracking in the plant production, thus improving the performance after hot rolling and coil grinding. said emptying of bars as casings of pilot product), whose compositions are listed in Table 20, show the beneficial effect of Cr in the prevention of cracking of the lamination. No hot and therefore improved performance. Table 21 lists the performance of the normalized emptying plant (CPY) of six bars containing Cr and four bars without Cr, where the normalized CPY is obtained as follows: First the individualized CPY is calculated as the ratio of the weight of grinding of bovine to the weight of the bar emptied. Second the bar with the highest CPY, in this case RN 033410, is assigned a normalized CPY of 100%. Third, the standardized CPY of all other bars are calculated by dividing the CPY of each bar by the CPY of R 033410. The normalized CPY of the bars without Cr is 48-82% comparing to 82-100% for bars containing Cr.

The level limit of Cr would be desirable due to the abrasiveness of the Cr silicas which is demonstrated in Figure 26. Figure 26A shows the wear on a steel ball tool that is. slid 3000 linear inches (1500 inches on each side of the strip) under a load of 100 gm onto the strip surface with butter oil as a lubricant from a sample without Cr (RN033407) that was annealed in plant solution at 975 ° C, cold rolled 25% then aged at 450 ° C and cleaned with sulfuric acid, while Figure 26B has a similar condition using a sample of an alloy containing Cr (RN834062). The polished appearance of the ball shown in 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 the stamping of a sheet of the alloy into parts, a high amount of wear would occur. of the tool.

Table 19 Alloys used in Example 9 Alloy Ni Co Cr Si Mg K224 3.71 0.91 0 1.14 - K225 3.71 0.93 0.11 1.19 0.030 K226 3.61 0.82 0.23 1.20 0.035 K227 3.50 0.95 0.34 120 0.035 K228 3.51 0.85 0.46 121 0.040 229 3.39 0.85 0.55 1.20 0.043 A single pour run produced three bars with the composition shown in Table 21a. The performance of the bar emptying plant, which is similarly normalized to the data in Table 21 where RN033410 is considered 100%, is given in Table 21b. The CPY of the bars with low Cr compares favorably with the bars containing Cr of Table 21. This is believed to be due to the cracking of Cr reduction during the hot rolling even at these low levels. The RN037969 has a CPY% normalized above 100 due to the fact that the performance of this bar was higher than RN033410 in the previous example.

Example 10 - Effect of Cr, n A series of ten-pound laboratory ingots with the compositions listed in Table 22 were fused in a crucible of silica and were emptied in Durville form in steel molds, which after the ligation were approximately 4"X 4" X 1.75"Figure 27 is a flow chart of the process of this Example 10. The K259 alloy contains a smaller nickel of Cr than those alloys in Example 9, to investigate the lower limits1 on the beneficial effect of Cr in hot rolling.The alloys K251, K254 and K260 contain low levels of Mn, to determine whether the Mn affects the hot rolling in the alloy of this invention.The ingots were then machined to have tapered edges, as schematically illustrated in Fig. 23, to create a higher state of tensile stress at the edges. they soaked for two hours at 900 ° C, and were rolled in two steps at 1.12"(1.4" / 1.12") then cooled with water. After an examination for cracks, the bars were reheated at 900 ° C for two hours, and rolled in three steps at 0.50"(0.9" / 0.7"/ 0.5"), followed by cooling with water. The K259, with 0.058% Cr, is hot rolled without the formation of edge cracks. The alloys containing ??, · together with K261 (neither with Cr nor Mn) developed large edge cracks. In this way, an addition of Cr close to 0.05%, with a preferred range of 0.025 to 0.1% Cr, seems to be appropriate for the hot rolling equilibrium and formation of abrasive particles that would lead to wear of the tool.

The cooled bars were then soaked at 590 ° C for 6 hours, cut and then ground to remove the surface oxides developed during hot rolling. The alloys were then cold rolled to 0.012"and heat treated in solution in a fluidized bed furnace for 60 seconds at 950 ° C. The alloys were then annealed for aging at 475 ° C for 3 hours. Designed to increase strength and conductivity, these alloys were then cold rolled from 25% to 0.009"and aged at 300 ° C for 3 hours. Alternatively, after heat treatment in solution the alloys were cold rolled from 25% to 0.009", giving an annealing by aging at 475 ° C for 3 hours, cold rolled from 22% to 0.007", and annealing was given end of 300 ° C for 3 hours. The properties after final aging for both process routes are listed in Table 23. For both processes, the combination of · exceptionally good property of deformation yield of 150 ksi and at least 31% of IACS was achieved, with low levels of Cr, Mn or none. Conductivity and strain resistance are plotted in Figures 28 and 29 against the stoichiometric ratio ((Ni + Co) / (Si-Cr / 5)) together with the data from the Example 8 to demonstrate the unusually good properties achieved when the relationship is maintained between 3.0 and 5.0.

^ Relationship = (Ni + Co) / (Si-Cr / 5) Example 11 - Effect of Processing Sections of the plant emptying bar RN032037, whose composition is in Table 20, were processed from the cold-rolled and ground-ground plate by a 0.600-in. Thick plant borehole.The samples were further processed by a variety of routes. processing shown in Fig. 30. Process A involved cold rolling at 0.012"and heat treatment in solution in a fluidized bed furnace for 60 seconds at 950 ° C, annealing by aging at 500 ° C for 3 hours. hours, cold rolling from 25% to 0.009", and giving a second anneal at 350 ° C for 4 hours.In process B, the metal was rolled at 0.050" and gave an intermediate bell annealing ("I BA") of 575 ° C for 8 hours. Then the samples were subjected to cold rolling at 0.012"and to heat treatment in solution in a fluidized bed furnace for 60 seconds at 950 ° C, annealing by aging at 500 ° C: for 3 hours, cold rolling 25% to 0.009", and giving a second anneal at 350 ° C for 4 hours. In process C, the alloy was laminated to 0.024"and treated with heat in solution in a fluidized bed furnace for 60 seconds at 950 ° C, followed by cold rolling at 0.012" and a second heat treatment in solution in a fluidized bed furnace for 60 seconds at 950 ° C. Subsequently, the process involved annealing, by aging at 500 ° C for 3 hours, cold rolling from 25% to 0.009", and giving a second anneal at 350 ° C for 4 hours.In process D, cold rolling at 0.012"was followed by the heat treatment in solution in a fluidized bed furnace for 60 seconds at 950 ° C the alloy was cold rolled from 25% to 0.009", giving an annealing at 475 ° C for: 3 hours, cold rolled from 22% to 0.007", and gave a final annealing of 300 ° C for 3 hours. In process E, the metal was laminated to 0.050"and gave an intermediate bell anneal of 575 ° C for 8 hours, then the samples were laminated to 0.024" and heat treated in solution in a fluidized bed furnace during 60 seconds at 950 ° C, followed by cold rolling of 0.012" and a second heat treatment in solution in a fluidized bed furnace for 60 seconds at 950 ° C. Subsequently, the process involved annealing at 500 ° C for 3 hours, cold rolling from 25% to 0.009", and giving a second anneal at 350 ° C for 4 hours.

Example 12 Effect of Processing The sections of the plant emptying bar RN032037, whose composition is in Table 20, were processed from the hot rolled and ground plate by bovine plant of 0.600"thickness.The process variables were systematically varied to explore a matrix , which contains ranges of processing conditions Figure 31 is a flow chart of the process of this Example 12. After cold rolling at 0.012", the samples were annealed in solution in a fluidized bed furnace at temperatures of 925 , 950, 975 and 1000 ° C for 60 seconds. The samples were then annealed by aging at temperatures of 450, 475, 500 and 525 ° C for three hours. The samples were then cold-rolled to a final thickness in 15, 25 and 35% variant reductions. Finally, at Samples were given a second annealing by aging for four hours at 300, 325, 350 and 375 ° C. Table 25 contains properties of the samples with different annealing temperatures in solution while the rest of the process remained constant. As the solution temperature increases, the deformation resistance increases, while the conductivity decreases. Additionally, bending formability is worsened at higher solution annealing temperatures, due to the large grain size developed during annealing at 975 and 1000 ° C. In this way an annealed grain size in solution below 20 μ ?? is preferred.

When the temperature of the first aging is varied while the other processing variables remain constant, it was discovered that the highest resistance levels are due to the intermediate aging temperatures, as shown for the ages of 475 and 500 ° C in Table 26. Also, the conductivity increased with the increase in aging temperature. In this way, the first aging temperature can be manipulated to provide various desirable combinations of strength and conductivity.

When the reduction of the lamination between the first and second aging was varied, the resistance of deformation was found to be increased with the increase of the reduction, in this case, up to 35%, while, that the conductivity was not affected. It is discovered a greater increase in resistance to go from 15 to 25% reduction than when going from 25 to 35%. It was found that the fold formability is worsened with higher reductions. The reduction of the lamination is manipulated to affect the resistance-formability characteristics of the material produced. The use of lamination reduction above 35% can be useful to produce a peak resistance, although with more deficient formability.

Table 28 shows that the second annealing temperature by aging does not have a large effect on the properties when the other processing variables are kept constant. It was found that the conductivity increases as the temperature of the second aging increases, but to a small degree. In this way a wide range of operation is acceptable for this stage of the process. ' Table 25 Effect of the variation of annealing temperatures in solution, with a first aging at 475 ° C, 25% reduction of lamination, second aging at 350 ° C of Example 12 temperature SA, ° C grain size um YS TSIB% of IACS Folds of 90 ° i 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 26.8 147.5 / 152.1 / 3 32.7 8.7 / 12.1 Table 26 Effect of the variation of the first aging temperatures, with annealing in solution at 950 ° C, 25% reduction of lamination, second aging at 350 ° C of Example 12 Temp. of the 1st Envy, "C YS / ÍS / EI% of IACS Folds of 90 ° 450 140.1 / 14534 30.5 4.0 8.1 47S 145.9 / 152.3 / 3 34.1 6.1 / 8.1 500 145.1 / 152.7 / 3 36.2 4.07.0 525 133.2 / 134.5 / 1 39.9 n / m * measured value Table 27 Effect of the variation of the lamination reductions, with annealing in solution at 950 ° C, first aging at 475 ° C, second aging at 350 ° C Reduction of lamination YS / TS / EI% of IACS Folds of 90 ° 15% 138.4 / 145.0 / 4 33.9 5.4 / 5.4 25% 145.9 / 152.3 / 3 34.1 6.1 / 6.1 35% 148.9 / 155-6 / 3 34.0 7.1 / 10.0 Table 28 Effect of the variation of the temperatures of the second aging, with annealing in solution at 950 ° C, first aging at 475 ° C, 25% reduction in lamination m Temp. of the 2nd Enviro, ° C YS / TS / EI% of IACS Folds of 90 ° 300 146.4 / 152.0 / 2 33.2 6.1 / 15.1 325 146.6 / 152.3 / 3 33.6 5.1 / 8.7 350 145.9 / 152.3 / 3 34.1 6.1 / &; 1 - 375 148.2 / 152.7 / 3 34.8 6.08.6 Samples from the bar emptied into plant without Cr RN033407 (composition in Table 20) were laminated in the laboratory of the condition of grinding by bovine at 0.460"below 0.012". Subsequently the samples were heat treated in solution in a fluidized bed furnace for 60 seconds at 900 ° C. The samples were then laminated 25% to 0. 009"and were annealed by aging at 425, 450 and 475 ° C for 4 and 8 hours at each temperature, subsequently the samples were cold rolled from 22% to 0.007" and gave a final annealing of 300 ° C for three hours. The best combination of resistance and conductivity resulted from aging at 450 ° C for 8 hours, with the properties of that condition and others listed in Table 28a. Comparing the data of 450 ° C / 8 hr with the properties in Table 25, it is clear that the further reduction of the annealing temperature in solution at 900 ° C decreases the deformation resistance and increases the conductivity to produce the unique combination of 140 ksi and 39% of IACS. In addition, the processing that includes an annealing temperature in solution of 900 ° C produced an improved bending formability when compared to the processing that involves higher solution annealing temperatures.

Example 13 - Effect of Si and Mg Laboratory ingots with the compositions listed in Table 29 were melted in a graphite crucible and emptied in Tamman form into steel molds, which after the tapping were 4.33"X2.17" X1.02". alloys were objective to have a content. of Cr of 0.5%. The content of Si was varied between 1.0% and 1.5%. For variants of 1.5% with high Si the Ni / Co ratio varied between 4.98 and 11.37 with a stoichiometric ratio; fixed ((Ni + Co) / (Si-Cr / 5)) of approximately 4. The influence of Mg it was tested by the BW alloy with the same alloy composition as BV but with additionally 0.1% Mg. , Figure 32 is a flow chart of the process of this Example 13. After soaking for two hours at 900 ° C, they were hot rolled at 0.472", whereby they were reheated after each step at 900 ° C for 10 minutes. After the last step the bar was cooled with water.After trimming and grinding at 0.394"in order to remove the surface oxide, the alloys were: cold rolled to 0.012" and treated with heat in solution in a fluidized bed furnace for the time and temperature listed in Table 29. It selected the time and temperature to achieve the aba'jo grain sizes of 20 μp ?.

Subsequently, the alloys were cold rolled from 25% to 0.009"and then annealed for 450 and 475 ° C aging for 3 hours.The properties of the samples are listed in Table 30. The formability was measured by the via the V-shaped block. With the increase in content If the resistance of deformation is increased from 121 ksi for the 1.05% Si alloy to 135 ksi for the 1.51% Si alloy. / For variants of 1.16% Si of Mg, this results in a benefit to the deformation resistance of 5-7 ksi. The decrease in the Ni / Co ratio from 11.37 to 4.98 improves the deformation resistance for high Si (1.5%) alloys. The stress relaxation was tested by the ring method with an objective initial tension of 0.8 times of strain resistance. Table 31 shows the stress relaxation data for the BV, BW and BX variants. The comparison of BV and BW, due to the addition of Mg the stress relieving resistance increases from 66.3% to 86.6% for the condition of 150 ° C / 1000h and from 48.5% to 72.3% for the condition of 200 ° C / 1000h. The stress relieving resistance of the Si-containing BX amounts higher to 82.3% for the condition of 150 ° C / 1000h and 68.7% for the condition of 200 ° C / 1000h.

Table 29 Alloys of Examples 13 and 15,% by weight *) Ratio = (Ni + Co) / (Si-Cr / 5): Table 30 Properties for the SA-Cr-AA Process of Example 13 Example 14 - Effect of Si and Mg Figure 33 is a flow chart of the process of this Example 14. The specimens of Example 13 were cold-rolled subsequently to 0.007"with a cold reduction of 22%, then the samples were annealed by aging at temperatures of 300 ° C. at 400 ° C for 3 hours The properties of the samples that gave | second aging at 300 ° C are listed in Table 32. formability was measured via the V-shaped block.

The highest deformation resistance was achieved with a first aging temperature of 450 ° C. With the increase of the Si content the deformation strength is increased from 131 ksi for the 1.05% Si alloy to 147 ksi for the 1.51% Si alloy. For the variants of 1.16% Si of Mg results in a benefit to the deformation resistance of 7-10 ksi. The decrease in the Ni / Co ratio from 11.37 to 4.98 improves the deformation resistance for the alloys of 1.5% Si high by 3 ksi. The stress relaxation was tested by the ring method with an initial target tension of 0.8 times the strain resistance. Table 33 shows the stress relaxation data for BV, BW and BX for the SA-CR-l.AA process 450 ° C - CR - 2.AA 300 ° C.

Comparing BV and BW, due to the addition of Mg, the stress relaxation resistance increases from 72.6% to 85.6% for the condition of 150 ° C / 1000h and from 55.8% to 69.3% for the condition of 200 ° C / 1000h. The stress relieving resistance of the quantities of BX containing Si higher to 81.1% for the condition of 150 ° C / 1000h and 66.1% for the condition of 200 ° C / 1000h.

Table 32 Properties of Process SA-CR-1AA-CR-2AA of Example 14 Alloy 2.AA 300 ° C / 31 1. AA T, ° C YS, ksi TS, ksi A10,%% of IACS 90 ° MINBR / t BU 450 130.7 138.1 2.6 33.6 5.5 / 5.5 450 137.4 144.5 3.7 31, 4 2.8 / 5.6 BV 475 130.8 137.8 4.8 34.8 2.8 / 5.0 450 144.0 143.6 2.3 32.1 3.3 7.8 BW 475 141, 3 147.1 3.8 34 2.8 / 6.7 450 144.6 152.4 2.9 29.8 4.0 / 8.0 BT 475 137.8 146.2 4.2 34.1 4.0 / 7.0 450 143.7 155.2 2.8 28.6 3.3 / 7.8 BX 475 134.4 148.2 2.8 31, 2 2.8 / 6.7 450 146.6 155.8 3 29.6 3.3 / 6.7 BY 475 137.8 150.0 4.3 32.2 3.3 / 6.7 Table 33 Stress Relaxation Process SA-CR-1AA450 ° C-CR-2AA300 ° C of Example 14 Example 15: Effect of Si and Mg Laboratory ingots with the compositions listed in Table 34 were melted in a graphite crucible and emptied in Taiman form in steel molds, which after the lining were 4.33"X2.17" X1.02". without Cr and with a stoichiometric ratio ((Ni + Co) / (Si-Cr / 5)) of approximately 4.2 The Ni / Co ratio was approximately 4.5 The alloys have an objective Si content of 1.1%, but the variant Mg content and an alloy have a Si content of 1.4% and additionally Mg. Figure 34 is a flow chart of the process of this Example 15. After soaking for two hours at 900 ° C, they were hot rolled to 0.472", whereupon they were reheated after each step at 900 ° C for 10 minutes, after the last step the bar was cooled with After trimming and grinding at 0.394"in order to remove the surface oxide, the alloys were cold rolled at 0.012" and treated with heat in solution in a fluidized bed furnace for the time and temperature listed in Table 34 Was the time and temperature selected to achieve grain sizes below 20 μp? Subsequently, the alloys were cold rolled from 25% to 0.009"and then annealed for 450 and 475 ° C aging for 3 hours.The properties of the samples are listed in Table 35. The deformation strength, measured formability with the V-shaped block and conductivity of FL and FM without Cr are similar to the BV and BW containing Cr of Example 13, with the comparable Si content of 1.1%, Ni / Co ratio and stoichiometric ratio. Example 13, an addition of 0.1% Mg results in a benefit to the deformation strength of 7-8 ksi.

With the Si content increase from 1.17% to 1.39% the deformation resistance increases from 126.6 to 130.5 ksi at the same annealing temperature in the solution. For the variant FN, the increase in the temperature of Annealing in solution of 950 ° C to 1000 ° C results in an increase in deformation resistance of 10 ksi.

The stress relaxation was tested by: the ring method with an objective initial tension of 0.8 times of strain resistance. Table 36 shows the stress relaxation data for the processes with the solution annealing temperature of 950 ° C. Compared with the 1.16% Si samples containing Cr from Example 13, BV and BW, the relaxation of. the 'FL and FM voltage is slightly lower. Similar to Example 13, an addition of 0.1% Mg results in an increase in stress relaxation from 64.6% to 82.7% at the condition of 150 ° C / 1000h and from 44.3% to 69.2% for the condition of 200 ° C / 1000h. The tensile relaxation resistance of the variant amounts of FN of 1.39% Si, which contains Mg at 84.1% for the condition of 150 ° C / 1000h and 65.9% for the condition of 200 ° C / 1000h.

*) Ratio = '(Ni + Co) / (Si-Cr / 5) Table 35 Properties of the SA-CR-AA Process of Example 15 Table 36 Process Stress Relaxation SA 950 ° C: - CR 25% - AA 450 ° C / 3h of Example 15 Example 16: Effect of Si and Mg Figure 35 is a flow chart of the process of this Example 16. The specimens of Example 15 were cold rolled subsequently to 0.007"with a cold reduction of 22%, then the samples were annealed by aging at temperatures of 300 ° C. at 350 ° C for 3 hours The properties of the samples that gave second aging at 300 ° C are listed in Table 37. The formability was measured via the V-shaped block, the deformation resistance was achieved more high with a first temperature of 450 ° C.

The FM shows a higher deformation resistance of 11 ksi in comparison with the FL, which is partially ascribed to the Mg content and is partially ascribed to the slightly higher Si content. The deformation resistance, bending capacity and conductivity of the FL and FM without Cr are similar to the BV and BW containing Cr of Example 15, with the comparable Si content, ratio of | Ni / Co and stoichiometric ratio.

The increase in Si content from 1.17% to 1.39% leads to the same deformation strength of approximately 144 ksi for an annealing temperature in solution of 950 ° C. For the FN variant, the increase in the annealing temperature in solution from 950 ° C to 1000 ° C results in an increase in the deformation resistance from 143 to 158 ksi.

The tension relaxation was tested by the ring method with an initial target tension of strain resistance times. Table 38 shows FL and FM voltage relaxation data for SA processes 950 ° C - CR - 1AA 450 ° C - CR - 2.AA 300 ° C. Compared with the Si samples at 1.16% containing Cr of Example 15, the BV and BW, the relaxation of the FL and FM tension is lower by 2-3%. Similar to Example 15, an Mg addition of 0.1% results in an increase in stress relaxation from 70.0% to 82.0% for the condition of 150 ° C / 1000h and from 52.3% to 66.9% "'for the ^ rate of 200 ° C / 1000h: the tensile strength of the variant amounts of FN of 1.39% Si, which contain Mg at 85.0% for the condition of 150 ° C / 1000h and 66.4% for the condition of 200 ° C / 1000h.

Table 37 Properties for the SA-CR-1AA-CR-2AA Process of Example 16 Table 38 Process Stress Relaxation SA 950 ° C-CR-1AA 450 ° C-CR-2AA 300 ° C of Example 16 Figure 36 shows the relationship between 90 ° -minBR / t BW and the deformation resistance for the alloys and processes of Examples 13, 14, 15, and 16. Both SA-CR-AA and SA-CR-AA-CR-AA processes form two groups, with a certain formability ratio - deformation resistance. The solid lines are only a guide for the eye and mark the increase of in BR / t and mark the formation resistance with the higher Si content and / or Mg addition. There is almost no difference in the deformation resistance and the formability-resistance ratio of deformation between the variants containing Cr and without Cr.

Figure 37 shows the relationship between the%, IACS and the deformation strength for the alloys and processes of Examples 13, 14, 15, and 16. The non-Cr and Cr-containing alloys show the same ability to achieve a 30% conductivity of IACS together with high deformation resistance. The process SA - CR - AA - CR - AA achieves a higher deformation resistance than the SA - CR - AA process, but in the same conductivity.

Claims (31)

1. A copper base alloy having an improved combination of deformation resistance and electrical conductivity, characterized in that it consists essentially of: between about 1.0 and about 6.0 weight percent Ni; up to about 3.0 weight percent Co; between about 0.5 and about 2.0 weight percent Si; between about 0.01 and about 0.5 weight percent g; up to about 1.0 weight percent Cr; up to about 1.0 weight percent Sn, and up to about 1.0 weight percent Mn, the remainder being copper and impurities, the processed alloy has a deformation strength of at least about 137 ksi, and an electrical conductivity of at least about 25% of IACS.

2. The alloy according to claim 1, characterized in that the alloy has a conductivity of at least about 30% IACS.

3. The alloy according to claim 1, characterized in that the alloy is processed to have a deformation strength of at least about 137 ksi, and an electrical conductivity of at least about 38% IACS.

4. The alloy, according to claim 1, characterized in that the alloy is processed to have a deformation strength of at least about 143 ksi, and one, electrical conductivity of at least about 37% IACS.

5. The alloy according to claim 1, characterized in that the alloy is processed to have a deformation strength of at least about 157 ksi, and an electrical conductivity of at least about 32% IACS.

6. A copper base alloy having an improved combination of deformation resistance and electrical conductivity, characterized in that it consists essentially of: between about 1.0 and about 6.0 weight percent Ni; up to about 3.0 weight percent Co; between about 0.5 and about 2.0 weight percent Si; between about 0.01 and about 0.5 weight percent Mg; up to about 1.0 weight percent Cr; up to about 1.0 weight percent of Sn, and up to about 1.0 percent by weight of Mn, the rest which is copper and impurities, the processed alloy has a deformation strength of at least about 137ksi, and a mbr / t of less than 41 for both good-folds and bad-folds.

7. The copper base alloy according to claim 6, characterized in that the alloy has a mbr / t of less than about 2 t for both good folds and badly folds.

8. The copper base alloy according to claim 6, characterized in that the alloy has an electrical conductivity of at least about 25% IACS.

9. The copper base alloy according to claim 8, characterized in that the alloy has a conductivity of at least about 30% IACS.

10. A copper base alloy having an improved combination of deformation resistance, electrical conductivity and formability, characterized in that it consists essentially of: between about 1.0 and about 6.0 weight percent Ni; 1 to about 3.0 weight percent Co; between about 0.5 and about 2.0 percent in Yes weight; 'between about 0.01 and about 0.5 weight percent g; up to about 1.0 weight percent Cr; up to about 1.0 weight percent Sn, and up to about 1.0 weight percent Mn, the remainder being copper and impurities, the ratio of (Ni + Co) / (Si-Cr / 5) which is between about 3 and about 7.

11. The alloy according to claim 10, characterized in that the alloy has a mbr / t of less than about 4 t for both good-shape bends and badly folds.

12. The alloy in accordance with. claim 10, characterized in that the alloy has a mbr / t of less than about 2 t for both folds in good way and bends in a bad manner.

13. The alloy according to claim 10, characterized in that the alloy is processed to have a deformation resistance of at least about 137 ksi, and an electrical conductivity of at least about 38% of IACS.

14. The alloy according to claim 10, characterized in that the alloy is processed to have a deformation resistance of less about 137 ksi, 'and an electrical conductivity of at least about 37% IACS.

15. The alloy according to claim 10, characterized in that the alloy is processed to have a deformation strength of at least about 157 ksi, and an electrical conductivity of at least about 32% of IACS.

16. The copper base alloy according to claim 1, characterized in that the alloy is in the form of thin sheet, wires, bar or tube.

17. A copper base alloy having an improved combination of deformation resistance and electrical conductivity, characterized in that it consists essentially of: between about 3.0 and about 5.0 weight percent Ni; up to about 2.0 weight percent Co; between about 0.7 and about 1.5 weight percent Si; between about 0.03 and about 0.25 weight percent Mg; to about 0.6 weight percent Cr; : up to about 1.0 weight percent Sn, and up to about 1.0 weight percent Mn, the rest that is copper and impurities, the ratio of (Ni + Co) / (Si-Cr / 5) which is between about 3 and about 7.

18. A copper base alloy having an improved combination of deformation resistance and electrical conductivity, characterized in that it consists essentially of: between about 3.0 and about 5.0 weight percent Ni; up to about 2.0 weight percent Co; between about 0.7 and about 1.5 weight percent Si; between about 0.03 and about 0.25 weight percent Mg; to about 0.6 weight percent Cr; up to about 1.0 weight percent Sn, and up to about 1.0 weight percent Mn, the remainder being copper and impurities, the processed alloy has a deformation strength of at least about 137 ksi, and an electrical conductivity of at least about 25% of IACS.

19. The alloy according to claim 18, characterized in that the alloy is processed to have a deformation resistance of at least about 137 ksi, and an electrical conductivity of at least about 38% of IACS.

20. The alloy according to claim 18, characterized in that the alloy is processed to have a deformation strength of at least about 143 ksi, and an electrical conductivity of at least about 37% IACS.

21. The alloy according to claim 18, characterized in that the alloy is processed to have a deformation strength of at least about 157 ksi, and an electrical conductivity of at least about 32% IACS.

22. A copper base alloy having an improved combination of deformation resistance and electrical conductivity, characterized in that it consists essentially of: between about 3.5 and about 3.9 weight percent Ni; between about 0.8 and about 1.0 weight percent of Co; between about 1.0 and about 1.2 weight percent Si; between about 0.05 and about 0.15 weight percent Mg; to about 0.1 weight percent Cr; up to about 1.0 weight percent Sn, and up to about 1.0 weight percent Mn, the remainder being copper and impurities, the processed alloy has a deformation strength of at least about 140ksi, and an electrical conductivity of at least about 30% IACS.

23. The alloy according to claim 22, characterized in that the ratio of (Ni + Co) / (Si-Cr / 5) is between about 3.5 and about 5.0.

24. The alloy according to claim 23, characterized in that the Ni / Co ratio is between about 3 and about 5.

25. The alloy according to claim 22, characterized in that the Ni / Co ratio is between about 3 and about 5.

26. A process for making a copper base alloy including nickel, silicon, cobalt and chromium, characterized in that it comprises: melt and empty the alloy; hot rolled from about 750 ° to about 1050 ° C; cold rolled to a suitable size for solution formation; annealing the alloy in solution, between about 800 ° and about 1050 ° C about 10 seconds to about one hour; Y subsequently quenching or quenching the alloy rapidly at room temperature to obtain an electrical conductivity of less than about 20% IACS (11.6 MS / m) and an equidimensional grain size of about 5-20 Ppi; Cold rolling the alloy for a reduction, from 0 to about 75% in thickness; subjecting the alloy to a hardening anneal of about 300 ° to about 600 ° C for about 10 minutes to about 10 hours; subsequently cold rolling the alloy by a reduction from about 10 to about 75% in thickness to a finishing gauge; subjecting the alloy to a second aging hardening anneal from 250 to about 500 ° C for about 10 minutes to about 10 hours to achieve this.

27. The process according to claim 26, characterized in that it also comprises an intermediate recrystallization annealing after hot rolling.

.28. The process according to claim 26, characterized in that the alloy consists essentially of between about 1.0 and about 6.0 percent in Ni weight; up to about 3.0 weight percent Co; between about 0.5 and about 2.0 weight percent Si; between about 0.01 and about 0.5 weight percent Mg; up to about 1.0 weight percent Cr; up to about 1.0 weight percent Sn / and up to about 1.0 weight percent Mn, the rest that is copper and impurities.

29. The process according to claim 28, characterized in that the alloy consists essentially of: between about 3.0 and about 5.0 weight percent Ni; up to about 2.0 weight percent Co; between about 0.7 and about 1.5 weight percent Si; between about 0.03 and about 0.25 weight percent Mg; to about 0.6 weight percent Cr; up to about 1.0 weight percent Sn, and up to about 1.0 weight percent Mn, the rest; which is copper and unavoidable impurities.

30. The process in accordance with the claim 29, characterized in that the ratio of (Ni + Co) / (Si-Cr / 5) which is between about 3 and about 7.:

31. The process according to claim 29, characterized in that the alloy comprises between about 3.5 and about 3.9 weight percent Ni; between about 0.8 and about 1.0 weight percent of Co; between about 1.0 and about 1.2 weight percent Si; between about 0.05 and about 0.15 weight percent Mg; to about 0.1 weight percent Cr; up to about 1.0 weight percent Sn, and up to about 1.0 weight percent Mn, the rest that is copper and impurities.