ES2670425T3 - Copper-Nickel-Silicon Alloys - Google Patents

Abstract

A copper-based alloy that has an improved combination of yield strength, electrical conductivity, and resistance to stress relaxation, consisting of: 3.5 to 3.9 weight percent Ni; between 0.8 and 1.0 percent by weight of Co; between 1.0 and 1.2 percent by weight of Si; between 0.05 and 0.15 percent by weight of Mg; up to 0.1 weight percent Cr; up to 1.0 percent by weight of Sn, and up to 1.0 percent by weight of Mn, the remainder being copper and impurities, where the Ni / Co ratio is between 3 and 5, the alloy being treated to have a yield point of at least 140 ksi (965 MPa) and an electrical conductivity of at least 30% IACS.

Description

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DESCRIPTION

Copper-Nickel-Silicon Alloys Background

This invention relates to copper-based alloys and, in particular, to copper-nickel-silicon based alloys.

Copper-nickel-silicon-based alloys are widely used for the production of electrically conductive parts of high mechanical strength, such as connectors and connection grilles. The C7025 alloy, developed by Olin Corporation, is an important example of a copper-nickel-silicon-based alloy that provides good mechanical (elasticity limit 95 ksi - 110 ksi / 665 MPa - 758 MPa) and electrical (35 % IACS). See U.S. patents. Nos. 4,594,221 and 4,728,372, incorporated herein by reference. More recently, O70 Corporation and Wieland Werke have developed the C7035 alloy, a cobalt-modified copper, nickel and silicon alloy, which can provide even better mechanical properties (elasticity limit 100 ksi - 130 ksi / 689 MPa - 896 MPa) and electrical (40-55% IACS). See US Pat. No. 7,182,823, incorporated herein by reference.

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

Typically, the formability is evaluated by the folding test where copper bands fold 90 ° around a known radius mandrel. The roller folding test uses a roller to form the band around the mandrel. Alternatively, the V-groove block test uses the mandrel to push the band into an open die, forcing 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 band (t) is then indicated as mbr / t. The minimum bend radius is the smallest radius of the mandrel around which a visible seamless band can be folded with an increase of 10x to 20x. Generally, the mbr / t is indicated both for the folds in the favorable direction, defined because the folding axis is normal to the rolling direction, and for the folding in the unfavorable direction, defined because the folding axis is parallel to the direction of folding. lamination. It is considered that a mbr / t of up to 4t constitutes good formability, both for the folds in the favorable direction and for the folds in the unfavorable direction. A mbr / t of up to 2 is more preferred.

Electrical conductivity is typically measured as an IACS percentage. IACS refers to the international standard of annealed copper, which assigns a conductivity value of 100% IACS to 20 ° C to "pure" copper. Throughout this description, all electrical and mechanical tests are performed at room temperature, nominally 20 ° C, unless otherwise specified. The term "approximately" indicates that accuracy is not required and should be interpreted as ± 10% of the referred value.

Mechanical strength is usually measured by the elasticity limit. A high mechanical strength copper alloy has an elasticity limit greater than 95 ksi (655.1 MPa) and preferably greater than 110 ksi (758.5 MPa). As the caliber of the copper alloy formed into components decreases and the miniaturization of these components continues, the combination of resistance and conductivity, for a given tempering, becomes more important than the resistance or conductivity considered separately.

Ductility can be measured by elongation. A measure of elongation is elongation A10, which is the permanent elongation of the length of the caliber after cracking, expressed as a percentage of the length of the original caliber L0, where L0 is taken equal to 10 mm.

Tensile relaxation resistance is considered acceptable when it is at least 70% of the remaining reported voltage after the test sample is exposed to a temperature of 150 ° C for 3,000 hours, and at least 90% of the reported voltage remaining after the test sample is exposed at a temperature of 105 ° C for 1,000 hours.

Tensile relaxation resistance was measured by the ring method [Fox A .: Research and Standards 4 (1964) 480], in which a 50 mm long band is clamped on the outer radius of a ring of steel that starts the tension on the outer surface of the band. With exposure to high temperatures, elastic stresses change to plastic deformation. This procedure depends on the time, temperature and initial tension defined by the radius of the steel ring. The experiments were performed between 50 ° C / 96 h and 210 ° C / 384 h. After each annealing, the remaining curvature of the band was measured and the corresponding tension reduction was calculated according to [Major G.B .: Wire Industry 46 (1979) 421]. Using the Larson-Miller parameter, P, extrapolation of short duration experiments at higher temperatures, to long duration experiments performed at lower temperatures can be made [Boegel A .: Metail 48 (1994) 872].

Stress relaxation can also be measured using the lift-off method, as described in the ASTM (American Society for Testing and Materials) E328-86 standard. This test measures the reduction of tension in a sample of a copper alloy maintained at a fixed voltage for a few times

Up to 3,000 hours. The technique consists in restricting the free end of a cantilever beam to a fixed deflection and measuring the load exerted by the beam on the restriction as a function of time and temperature. This is done by holding the cantilever beam test sample in a specially designed test frame. The condition of the standard test is to load the cantilever beam with 80% of the elasticity limit for a remaining deformation 5 of 0.2% at room temperature. If the calculated deflection exceeds approximately 0.2 inch (5 mm), the initial tension is reduced until the deflection is less than 0.2 inch (5 mm) and the load is recalculated. The test procedure consists of loading the cantilever beam with the calculated value of the load, adjusting the threaded screw in the test frame to maintain deflection and locking the threaded screw in place with a nut. The load required to lift the cantilever beam from the threaded screw is the initial load. The test frame is placed in an oven set at the desired test temperature. The test frame is periodically removed, allowed to cool to room temperature and the load required to lift the cantilever screw from the threaded screw is measured. The percentage of the remaining tension in the logarithms of the selected times is calculated and the data is represented on paper for semi-logarithmic graphs, putting the remaining tension in ordinates (vertical) and the logarithm of time in abscissa (horizontal). Using the linear regression technique, a straight line is adjusted across the data. To produce the values of the remaining voltage at 1, 1,000, 3,000 and 100,000 hours, interpolation and extrapolation is used.

The stress relaxation resistance is sensitive to orientation, and can be indicated in the longitudinal direction (L), where the test is carried out at 0 ° with the longest dimension of the test sample in the rolling direction of the web, and the deflection of the test sample being parallel to the lamination direction of the web. The stress relaxation resistance can be indicated in the transverse direction (T), where the test is carried out at 90 ° with the longest dimension of the test sample perpendicular to the laminating direction of the web, and being deflection of the test sample perpendicular to the direction of lamination of the web.

Table 1 shows the mechanical and electrical properties of some of the commercially available copper alloys that have been considered in the invention:

 Table 1: Examples of properties of Cu-based alloys exempt from currently available Be

 Alloy

 Company Composition Electrical conductivity (% IACS) Elasticity limit ksi (MPa)

 C7025

 Olin Brass Cu + 3.0Ni + 0.60Si + 0.15Mg> 35 95-110 (655-758)

 EFTEC-75

 Furukawa Cu + 3.2Ni + 0.65Si + 0.5Zn + 0.50Sn 25 116 (800)

 EFTEC-23Z

 Furukawa Cu + 2.5Ni + 0.6Si + 0.5Zn + 0.03Ag 53 101-116 (696-800)

 EFTEC-97

 Furukawa Cu + 2,3Ni + 0,55Si + 0,5Zn + 0,15Sn + 0,1 Mg 40 110 (758)

 EFTEC-98

 Unknown Furukawa 38 104-136 (717-938)

 EFTEC-98S

 Furukawa Cu + 3.8Ni + 0.93Si + 0.48Zn + 0.18Sn + 0.13Mg + 0.3Cr 38 95-129 (655-889)

 K62

 Wieland Cu + 0.3Cr + 0.4Ni + 0.6Sn + 0.03Ti 52 100 (689)

 KLF-125

 Kobe Steel Cu + 3,2Ni + 0,70Si + 0,3Zn + 1,25Mn 35 100 (689)

 CAC-65

 Kobe Steel Cu + 3.2Ni + 0.70Si + 1.0Zn + 0.50Sn 46 94 (648)

 MAX 251

 Mitsubishi Shindo Cu + 2.0Ni + 0.50Si + 0.50Sn 45 89 (614)

 Max375

 Mitsubishi Cu + 2.85Ni + 0.7Si + 0.5Zn + 0.5Sn + 0.015Mg 42 91-116 (627-800)

 KLF-1

 Kobe Steel Cu + 3.2Ni + 0.70Si + 0.3Zn + 0.05Mn 55 88 (607)

 C7027

 Olin Brass Cu + 2.0Ni + 0.60Si + 0.60Fe + 0.50Sn> 40> 80 (> 552)

 C18080 / K88

 Olin / Wieland Cu + 0.5 Cr + 0.1 Ag + 0.08 Fe + 0.06 Ti + 0.03 Si 80 80 (552)

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 C18070 / K75

 Wieland Cu + 0.3 Cr + 0.1 Ti + 0.02 Si> 75 70 (483)

 PMC 102

 Poongsan Cu + 1,3Ni + 0,25Si + 0,05P 60 75 (517)

 C7035 / K57

 Olin / Wieland Cu + 1.4Ni + 1.1Co + 0.6Si> 45 110-130 (758-896)

 NKC388

 Nippon Mining Cu + 3.8Ni + 0.85 Si + 0.18Mg + 0.1Mn 35-45 112-125 (772-862)

 HCL 305

 Hitachi Cu + 2.5Ni + 0.5Si + 1.7Zn + 0.02P 42 87-102 (600-703)

 HCL 307

 Hitachi Cu + 3.0Ni + 0.7Si + 1.7Zn + 0.3Sn + 0.02P 35 102-112 (703-772)

No matter how good these alloys are and how widespread their use, there are applications where alloys with greater mechanical strength are required, and in particular with greater mechanical strength without sacrificing other desirable properties, such as conductivity, stress relaxation resistance and / or conformability. Although beryllium copper, due to its beryllium content, can provide high mechanical strength, they are not suitable for many applications. Among beryllium-free copper alloys, high mechanical strength (for example, an elasticity limit above 130 ksi / 896 MPa) is usually accompanied by a significant decrease in other desirable properties, particularly conformability.

U.S. Pat. 2007/0079456 describes a copper alloy with 1-2.5% by weight nickel.

Compendium

A copper-based alloy and a method for manufacturing a copper-based alloy according to the invention are provided in the claims.

One aspect of the present invention is a stabilizable curable copper-nickel-silicon based alloy that can be treated to manufacture a commercially useful product band for use in electrical connectors and interconnections for the automotive and multimedia industries, in particular, and for any other applications that require a high elasticity limit and a moderately high electrical conductivity in a band, plate, cable or casting. Another aspect of the present invention is a method of treatment for manufacturing a commercially useful product band for use in electrical connectors and interconnections for the automotive and multimedia industries and for any other application that requires a high elasticity limit and moderately electrical conductivity. high.

Preferred embodiments are provided in claims 2 and 4.

This alloy is treated to have an elasticity limit of at least about 140 ksi (965 MPa) and an electrical conductivity of at least about 30% IACS.

Preferably, the alloys are treated so that they have an elasticity limit of at least about 143 ksi (986 MPa) and an electrical conductivity of at least about 37% IACS.

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

The alloys and the treatment methods of the various embodiments provide copper-based alloys that have an improved combination of the elasticity limit and electrical conductivity and, preferably, also the resistance to stress relaxation. In particular, the alloys have a greater mechanical resistance and a greater resistance to stress relaxation than those previously achieved with Cu-Ni-Si alloys, while maintaining reasonable levels of conductivity.

Brief description of the drawings

Fig. 1 is a flow chart of the treatment of the alloys of Example 1; Fig. 2 is a flow chart of the treatment of the alloys of Example 2; Fig. 3 is a flow chart of the treatment of the alloys of Example 3;

Fig. 4 is a graph of the limit of elasticity versus conductivity, for the alloys of Example 3;

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Fig. 5 is a graph of the elasticity limit versus folding 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 plot of the limit of elasticity versus conductivity for the alloys of Table 5 treated by the SA-CR-stabilization-CR-stabilization procedure of Example 4;

Fig. 8 is a graph of the elasticity limit versus folding formability (MBR / t) for the alloys of Table 5 treated by the SA-CR-stabilization-CR-stabilization procedure of Example 4;

Fig. 9 is a flow chart of the treatment of the alloys of Example 5;

Fig. 10 is a graph of the limit of elasticity versus the Ni / Co ratio for non-chromium alloys having similar alloy levels to those in Example 5;

Fig. 11 is a flow chart of the treatment of the alloys of Example 6; Fig. 12 is a flow chart of the treatment of the alloys of Example 7;

Fig. 13 is a graph showing the effect of the stoichiometric ratio on the elastic limit on the copper-nickel-chromium-silicon alloys of Example 7;

Fig. 14 is a graph showing the effect of the stoichiometric ratio on the elastic limit on the copper-nickel-cobalt-silicon alloys of Example 7;

Fig. 15 is a graph showing the effect of the stoichiometric ratio on the limit of elasticity in the copper-nickel-chromium-cobalt-silicon alloys of Example 7;

Fig. 16 is a graph showing the effect of stoichiometric copper-nickel-chromium-silicon alloys of Example 7;

Fig. 17 is a graph showing the effect of the stoichiometric ratio of copper-nickel-cobalt-silicon alloys of Example 7;

Fig. 18 is a graph showing the effect of stoichiometric copper-nickel-chromium-cobalt-silicon alloys of Example 7;

Fig. 19 is a flow chart of the treatment of the alloys of Example 8;

Fig. 20 is a graph showing the effect of the stoichiometric ratio on the% IACS in the alloys of Example 8 treated by the SA-CR-stabilization-CR-stabilization method with stabilizations at 475 ° C / 300 ° C.

Fig. 21 is a graph showing the effect of the stoichiometric ratio on the elastic limit on the alloys of Example 8 treated by the SA-CR-stabilization-CR-stabilization method with stabilizations at 475 ° C / 300 ° C;

Fig. 22 is a flow chart of the treatment of the alloys of Example 9;

Fig. 23 is a schematic diagram of a tapered edge hot rolling test tube;

Fig. 24 is a photograph of the hot rolled K224 alloy (without Cr), showing large fissures at the edges;

Fig. 25 is a photograph of the hot rolled K225 alloy (0.11 Cr), which shows no fissures at the edges;

Fig. 26A is a photograph of the results of the wear test of the alloy tool without Cr RN033407; Y

Fig. 26B is a photograph of the result of the wear test of the alloy tool containing Cr RN834062.

Fig. 27 is a flow chart of the treatment of the alloys of Example 10;

Fig. 28 is a graph showing the effect of the stoichiometric ratio on the% IACS of Example 8 and Example 10 (low Cr and Mn alloys) treated by the SA-CR-stabilization-CR-stabilization method with stabilizations at 475 ° C / 300 ° C; Y

Fig. 29 is a graph showing the effect of the stoichiometric ratio on the elasticity limit in Example 8 and Example 10 (alloys with low Cr and Mn content) treated by the SA-CR- method

on the electrical conductivity in the on the electrical conductivity in the on the electrical conductivity in the

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stabilization-CR-stabilization with stabilizations at 475 ° C / 300 ° C; Fig. 30 is a flow chart of the treatment of the alloys of Example 11; Y

Fig. 31 is a flow chart of the treatment of the alloys of Example 12;

Fig. 32 is a flow chart of the treatment of the alloys of Example 13;

Fig. 33 is a flow chart of the treatment of the alloys of Example 14;

Fig. 34 is a flow chart of the treatment of the alloys of Example 15;

Fig. 35 is a flow chart of the treatment of the alloys of Example 16;

Fig. 36 is a graph of the MBR / t BW of a block with a V-groove at 90 °, against the elasticity limit for the alloys and the procedures of Examples 13, 14, 15 and 16; Y

Fig. 37 is a graph of% IACS, versus the elasticity limit for alloys and procedures of Examples 13, 14, 15 and 16.

Detailed description

There is a need in the market for alloys for copper bands with greater mechanical resistance and electrical conductivity, together with good resistance to stress relaxation. This combination of properties is particularly important for components that are formed in various electrical interconnections for use in multimedia electrical connector and terminal applications. Commercially available copper alloys, such as C510 (phosphor bronze), C7025, C7035, C17410 and C17460, are being used for their generally favorable combinations of mechanical strength and conductivity. However, although these alloys have adequate mechanical strength for most current applications, the continued tendency to miniaturize components requires copper alloys that offer high mechanical strength, in combination with reasonably good electrical conductivity and resistance. to reasonably good relaxation, along with a reasonable cost. It is also desirable to minimize or eliminate potentially toxic alloy elements, such as beryllium.

The alloys that are used for multimedia interconnections require high mechanical resistance to avoid damage during connector insertion and to maintain good contact force during service. For these applications, all that is required is a good, but not especially high, electrical conductivity, since the conductivity simply needs to be sufficient to carry a current signal, and the high levels necessary to avoid heating are not needed. excessive due to I2R in higher power applications. For these applications there are even more stringent requirements for mechanical stability at room temperature and at slightly elevated service temperatures, which are characterized by good resistance to stress relaxation at approximately 100 ° C, for example.

The alloy compositions of the preferred embodiments of this invention and the scheme used to treat finishing temperings, surprisingly, provide a highly desirable combination of properties to meet the needs of both automotive and multimedia applications, namely a strength. very high mechanics along with a moderately high conductivity; in particular, the alloys of the preferred embodiments of the present invention are capable of being treated in the form of product bands with combinations of the electrical elasticity / conductivity limit 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 the elasticity limit and electrical conductivity, and a good resistance to stress relaxation, together with modest levels of folding. Where optimal levels of elasticity limit (YS) and electrical conductivity are required, for example, a combination of YS of 140 ksi (965 MPa) / 30% IACS is necessary, a composition that is provided in claim 1.

Generally, when the alloy elements are substantially above the indicated upper limits, excessive thick second phases occur.

When the ratio (Ni + Co) / (Si-Cr / 5) is controlled between approximately 3.5 and approximately 5, the electrical conductivity and the alloy's elasticity limit are the highest. The Ni / Co ratio is optimal for the limit of elasticity and conductivity when it is controlled between approximately 3 and approximately 5.

Magnesium generally increases the resistance to stress relaxation and resistance to softening in finished products; It also increases the resistance to softening during the thermal annealing treatments of stabilization of the process. When the Sn is present at low levels, it generally provides a strengthening of the solid solution and also increases the resistance to softening during the thermal annealing treatments of stabilization of the process, without unduly damaging the conductivity.

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Low levels of Mn generally improve folding formability, although with a loss of conductivity.

The preferred embodiment of the process of the present invention comprises a fusion and a laundry; a hot rolling of 750 to 1,050 ° C, an optional rolling to remove rust, and an optional homogenization or intermediate bell annealing, a cold rolling to obtain the caliber suitable for solubilization, a solution annealing treatment at 800 -1.050 ° C for 10 seconds to one hour, followed by a quenching or rapid cooling in water at room temperature to obtain an electrical conductivity of less than approximately 20% IACS (11.6 MS / m) and an equiaxial grain size of approximately 5-20 pm; a reduction in thickness by cold rolling from 0 to 75% to obtain the finishing gauge; an annealing of hardening and stabilization at 300-600 ° C for 10 minutes to 10 hours; and, subsequently, an additional cold lamination to obtain a thickness reduction of 10 to 75% to the finishing gauge; and a second annealing of hardening and stabilization of 250 to 500 ° C for 10 minutes to 10 hours.

The resulting alloy can also be treated to obtain the finishing caliper, without using a solubilization heat treatment during the process, by using cycles of lower temperature bell annealing treatments with cold work intervention. In addition, one or more optional recrystallization anneals can be added to the process during the reduction of the hot rolled gauge to the appropriate thickness for solubilization.

The preferred scheme to give rise to an alloy with an elasticity limit of at least about

140 ksi (965 MPa) and a conductivity of at least approximately 30% IACS, involves solubilizing at approximately 900 to 1,000 ° C, cold laminating approximately 25%, stabilizing at approximately 450-500 ° C for 3-9 hours, laminating cold at approximately 20-25% until finishing gauge and stabilize at 300-350 ° C for 3-9 hours.

Although this description is particularly directed to a process for the manufacture of copper alloy bands, the alloys of the invention and the methods of the invention are equally suitable for the manufacture of other copper alloy products, such as metallized paper, wire , bars and tubes. In addition, methods other than conventional casting, such as band casting, powder metallurgy and spray casting, are also within the scope of the invention.

The alloys and methods of the preferred embodiments will be better understood from the following illustrative examples:

Example 1 - Increasing alloy levels increases mechanical strength; Cobalt replacement improves mechanical strength and conductivity.

A series of 10-pound (4.5 kg) laboratory ingots were melted in a silica crucible with the compositions indicated in Table 2, and Durville was applied to steel molds which, after opening, were approximately 4 "x 4" x 1.75 "(0.1 mx 0.1 mx 0.044 m). Fig. 1 is a flow chart of the procedure of this Example 1. After homogenizing them for two hours at 900 ° C, hot rolled in three passes at 1.1 "(28 mm) (1.6" / 1.35 "/ 1.1") (41 mm / 34 mm / 28 mm), reheated to 900 ° C for 10 minutes, and then hot rolled in three passes at 0.50 "(13 mm) (0.9" / 0.7 "/ 0.5") (23 mm / 18 mm / 13 mm), followed by tempering in water, followed by a tempering of homogenization or overstabilization at 590 ° C for 6 hours After grinding and milling to remove surface oxide, the alloys were cold rolled at 0.012 "(0.3 mm) and the solution was heat treated in an oven echoed during the time and temperature indicated in Table 2. The time and temperature were selected to achieve an approximately constant grain size. The alloys were then subjected to a stabilization annealing of 400 to 500 ° C for 3 hours, designed to increase mechanical strength and conductivity. The alloys were then cold rolled 25% at 0.009 ”(0.23 mm) and stabilized at 300 to 400 ° C for 4 hours. Table 3 shows the properties measured after the second stabilization annealing. The data indicate that the elasticity limit increased with increasing alloy levels, in ternary alloys J994 to J999, from 127 to

141 ksi (876 to 972 MPa) when Si levels varied from 0.8 to 1.3%, respectively. When comparing alloys J994, K001 and K002 to examine the effect of Co on alloys close to 0.8% Si, it was observed that the substitution of Co for Ni increased both the elasticity limit and the conductivity. When considering the replacement of Co by Ni in alloys with ~ 1.2% Si, the K003 alloy showed a decrease in the elasticity limit and an increase in conductivity, while the K004, compared to the J998, showed an increase in the elasticity limit and a decrease in conductivity.

Having a Ni / Co ratio of approximately 3 (K002 and K004) led to greater mechanical strength than the Ni / Co ratio of 1 (K001 and K003), particularly for a higher Si level. The Mn alloys, K011 and K012, show that the replacement of Mn by Ni improved the mechanical / folding resistance properties, but with a significant loss of conductivity. When alloys J994 were compared to K036 and K037, it became clear that Sn provides a solid solution reinforcement.

 Table 2: Alloys of Examples 1 and 2

 Alloy

 Composition analyzed,% by weight Annealing conditions in solution Grain size, pm

 J994

 Cu-3.33 Ni -0.81 Si 850 ° C -1 minute 11.2

 J995

 Cu -3.78 Ni-0.92 Si 900 ° C -1 minute 16.5

 J996

 Cu -4.17 Ni -1.03 Si 900 ° C -1 minute 22.1

 J997

 Cu -4.48 Ni -1.12 Si 900 ° C -1 minute 22.1

 J998

 Cu -4.88 Ni -1.24 Si 900 ° C -1 minute 12.9

 J999

 Cu -5.39 Ni-1.35 Si 900 ° C - 2 minutes 14.1

 K001

 Cu -1.65 Ni -0.82 Si -1.66 Co 1,000 ° C - 30 seconds 12.9

 K002

 Cu -2.56 Ni -0.80 Si -0.79 Co 950 ° C -1 minute 17.7

 K003

 Cu -2.45 Ni -1.23 Si -2.46 Co 1,000 ° C - 30 seconds 6.7

 K004

 Cu -3.70 Ni -1.22 Si -1.15 Co 1,000 ° C - 30 seconds 12.9

 K009

 Cu -1.74 Ni -0.78 Si -1.67 Mn 850 ° C - 30 seconds 28.2

 K010

 Cu -2.65 Ni -0.79 Si -0.79 Mn 850 ° C - 30 seconds 22.1

 K011

 Cu -2.51 Ni -1.19 Si -2.56 Mn 850 ° C -1 minute 9.1

 K012

 Cu -3.70 Ni -1.21 Si -1.19 Mn 850 ° C -1 minute 9.8

 K013

 Cu -3.22 Ni -0.81 Si -0.10 Cr 850 ° C -1 minute 12.6

 K014

 Cu -3.31 Ni -0.82 Si -0.18 Cr 850 ° C -1 minute 10.7

 K015

 Cu -4.82 Ni -1.21 Si -0.09 Cr 900 ° C -1 minute 15.5

 K016

 Cu -4.89 Ni-1.26 Si -0.18 Cr 900 ° C -1 minute 12.9

 K036

 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

 K040

 Cu -3.74 Ni -0.72 Si -0.08 Mg 850 ° C - 2 minutes 17.7

 K041

 Cu -3.78 Ni -0.76 Si -0.205 Mg 850 ° C - 2 minutes 18.6

 Table 3: Properties of the alloys of Examples 1 of the SA-stabilization-CR-stabilization procedure

 Alloy

 Stabilizations% IACS YS / TS / EI ksi / ksi /% (MPa / MPa /%) 90 ° MBR / t

 J994

 450/300 36.8 126.7 / 130.8 / 2 (873.6 / 901.8 // 2) 2.91 / 3.4

 J995

 450/300 35.5 130.8 / 134.7 / 1 (901.8 / 928.7 / 1) 3.2 / 6.7

 J996

 450/300 34.5 132.7 / 138.5 / 2 (914.9 / 954.9 / 2) 3.1 / 6.9

 J997

 450/300 33.7 135.3 / 139.3 / 2 (932.9 / 960.4 / 2) 3.7 / 6.7

 J998

 450/300 34.3 137.9 / 144.2 / 2 (950.8 / 994.2 / 2) 3.3 / 8.6

 J999

 450/300 34.2 140.9 / 147.1 / 2 (971.5 / 1.014.2 / 2) 3.4 / 6.7

 K001

 500/300 40.3 129.2 / 134.4 / 2 (890.8 / 926.7 / 2) - -

 K002

 500/350 40.5 130.3 / 135.8 / 2 (898.4 / 936.3 / 2) 3.8 / 5.2

 K003

 450/300 37.8 129.7 / 134.3 / 2 (894.3 / 926.0 / 2) 3.5 / 3.7

 K004

 450/300 28.4 145.3 / 150.8 / 2 (1,001.8 / 1,039.7 / 2) 5.1 / 6.8

 K009

 450/350 16.5 108.1 / 113.3 / 4 (745.3 / 781.2 / 4) - -

 K010

 450/300 22.9 127.1 / 131.3 / 2 (876.3 / 905.3 / 2) - -

 K011

 400/300 11.9 137.6 / 141.0 / 2 (948.7 / 972.2 / 2) 2.4 / 3.2

 K012

 400/300 17.0 135.4 / 140.4 / 2 (933.6 / 968.0 / 2) 2.4 / 3.7

 K013

 450/300 36.7 125.4 / 129.6 / 2 (864.6 / 893.6 / 2) -

 K014

 450/300 36.2 128.0 / 131.9 / 2 (882.5 / 909.4 / 2) -

 K015

 450/300 33.8 135.6 / 139.8 / 2 (934.9 / 963.9 / 2) 3.5 / 5.2

 K016

 450/300 32.4 136.0 / 140.4 / 2 (937.7 / 968.0 / 2) 3.3 / 5.2

 K036

 450/300 34.3 131.5 / 143.1 / 1 (906.7 / 986.6 / 1) 3.9 / 6.9

 K037

 450/300 30.8 135.2 / 147.1 / 2 (932.2 / 1.014.2 / 2) 3.5 / 6.8

 K040

 450/350 38.4 125.4 / 136.5 / 2 (864.6 / 941.1 / 2) - -

 K041

 450/350 37.7 123.7 / 135.5 / 1 (852.9 / 934.2 / 1) - -

Example 2 - Cobalt improves mechanical strength.

Selected alloys of Example 1 were heat treated in solution in a fluidized bed furnace for the time and temperature indicated in Table 2. Fig. 2 is a process flow diagram of this Example 2. Subsequently the alloys are 25% cold rolled to 0.009 "(0.23 mm) and then subjected to stabilization annealing of 400 to 500 ° C for 3 hours. After an additional cold reduction of 22% to 0.007" (0, 18 mm), the samples were annealed and stabilized at temperatures of 300 to 400 ° C for 3 hours. Table 4 shows the properties of the representative conditions. In many cases the folding properties were somewhat better, with mechanical strengths similar to those of the procedure of Example 1. The 10 additions of Co (K003 and K004) and Sn (K037) provided the highest increase in mechanical strength in the Alloys of this example.

 Table 4: Properties of the alloys of Examples 2 of the SA-CR-stabilization-CR-stabilization procedure

 Alloy

 Stabilizations% IACS YS / TS / EI ksi / ksi /% (MPa / MPa /%) 90 ° MBR / t

 J994

 450/300 38.3 130.0 / 134.3 / 2 (958.4 / 926.0 / 2) 2.3 / 3.7

 J997

 450/300 37.7 125.2 / 132.7 / 2 (863.2 / 914.9 / 2) 2.9 / 8.9

 J998

 400/300 28.8 128.4 / 134.0 / 2 (885.3 / 923.9 / 2) 3.1 / 4.0

 J999

 400/300 29.5 131.9 / 135.4 / 2 (909.4 / 933.6 / 2) 3.1 / 5.1

 K002

 450/300 35.1 125.0 / 129.2 / 1 (861.8 / 890.8 / 1) 2.4 / 4.9

 K003

 450/300 33.7 135.2 / 140.3 / 2 (932.2 / 967.3 / 2) 3.1 / 4.0

 K004

 450/300 31.9 134.4 / 139.7 / 2 (926.7 / 963.2 / 2) 3.7 / 6.7

 K014

 450/300 38.1 127.9 / 132.3 / 2 (881.8 / 912.2 / 2) 2.3 / 4.0

 K036

 450/300 36.0 129.2 / 131.8 / 1 (890.8 / 908.7 / 1) 3.1 / 3.9

5

10

fifteen

twenty

25

 K037

 450/300 32.0 135.2 / 139.8 / 2 (932.2 / 963.9 / 2) 3.3 / 4.7

 K040

 450/300 38.7 127.1 / 129.3 / 1 (876.3 / 891.5 / 1) - -

 K041

 450/300 38.4 132.4 / 136.4 / 1 (912.9 / 940.4 / 1) 3.6 / 4.7

Example 3 - Cobalt and chromium levels and ratio (Ni + Co) / (Si-Cr / 5).

A series of 10 pound (4.5 kg) laboratory ingots were melted in a silica crucible with the compositions indicated in Table 5 and Durville was applied to steel molds which, after opening, were of approximately 4 "x 4" x 1.75 "(0.1 mx 0.1 mx 0.044 m). Figure 3 is a flow chart of the procedure of this Example 3. After homogenizing them for two hours at 900 ° C, hot rolled in three passes at 1.1 ”(28 mm) (1.6" / 1.35 "/ 1.1") (41 mm / 34 mm / 28 mm), reheated to 900 ° C

for 10 minutes, and then hot rolled in three passes at 0.50 "(13 mm) (0.9" / 0.7 "/ 0.5") (23 mm / 18

mm / 13 mm), followed by water quenching. The water-hardened plates were homogenized at 590 ° C for 6 hours, roughened and then milled to remove surface oxides that arose during hot rolling. Then, the alloys were cold rolled at 0.012 "(0.3 mm) and heat treated in solution in a fluidized bed furnace, for 60 seconds, at the temperatures indicated in Table 5. The temperature was

selected to maintain a relatively constant grain size. Then the alloys underwent a

Annealing stabilization from 400 to 500 ° C for 3 hours, designed to increase mechanical strength and conductivity. The alloys were then cold rolled 25% at 0.009 ”(0.23 mm) and stabilized at 300 to 400 ° C for 4 hours. Table 6 shows the properties measured after the second stabilization annealing. From this data set, it was observed that the additions to an alloy based on Cu-Ni-Si, Co (K068), Cr (K072), or both Co and Cr (K070) achieved the best combinations of mechanical strength, conductivity and formability by folding. It was also observed that relatively high Si levels of 1.2% and higher were present in the samples that had the highest mechanical strength. Although there was some evidence of reinforcement with the Sn, this was accompanied by poor conformability by folding. In Table 5, it can be seen that the ratio (Ni + Co) / (Si-Cr / 5) was very close to 4 for most alloys, particularly for K068, K070 and K072. In addition, the Ni / Co ratio was close to 3 for the K068 and the K070. The elasticity limit was plotted against conductivity in Figure 4, and against the conformability by folding in Figure 5. The values for K068, K070 and K072 were highlighted to show their unusually good combination of properties.

 Table 5: Alloys of Examples 3 and 4

 Alloy

 Composition analyzed,% by weight Ratio (Ni + Co) / (Si-Cr / 5) Ni / Co Annealing temperature in solution Grain size | jm

 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 3.80 925 ° 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 -1.28 Co -1.27 Si - 0.31 Mn 4.02 2.99 950 ° C 8

 K065

 Cu -4.96 Ni -1.25 Yes -0.085 Mg 3.97 900 ° C 17

 K066

 Cu - 3.29 Ni - 0.84 Si - 0.33 Mn - 0.092 Mg 3.92 850 ° C 10

 K067

 Cu - 2.57 Ni - 0.83 Co - 0.83 Si - 0.082 Mg 4.10 3.10 950 ° C 21

 K068

 Cu - 3.80 Ni -1.21 Co -1.27 Si - 0.048 Mg 3.94 3, t4 975 ° C 12

 K069

 Cu - 3.42 Ni - 0.64 Si - 0.89 Sn - 0.062 Mg 4.07 875 ° C 28

 K070

 Cu - 3.83 Ni -1.29 Co -1.39 Si - 0.56 Cr 4.01 2.97 975 ° C 8

 K071

 Cu - 3.38 Ni - 0.95 Si - 0.54 Cr - 0.035 Mg 3.99 950 ° C 19

 K072

 Cu - 4.64 Ni -1.28 Si ■ 0.54 Cr - 0.078 Mg 3.96 950 ° C 17

 K073

 Cu - 3.52 Ni -1.07 Si -1.06 Cr - 0.047 Mg 4.10 950 ° C 14

 K074

 Cu -4.11 Ni -1.31 Si -1.01 Cr - 0.058 Mg 3.71 975 ° C 18

 K075

 Cu -4.71 Ni -1.29 Si -0.50 Cr -0.85 Sn 3.96 950 ° C 19

 K076

 Cu - 3.54 Ni -1.00 Si - 0.49 Cr -0.89 Sn 3.92 925 ° C 17

 Table 6 - Properties of the SA-stabilization-CR-stabilization procedure of Example 3

 Alloy

 Stabilizations% IACS YS / TS / EI ksi / ksi /% (MPa / MPa /%) 90 ° MBR / t

 K056

 450/300 25.7 142.7 / 148.4 / 2 (983.9 / 1.023.2 / 2) 8.7 / 8.7

 K057

 450/350 29.0 131.3 / 137.6 / 3 (905.3 / 948.7 / 3) 3.3 / 6.9

 K058

 450/300 24.5 142.8 / 149.0 / 2 (984.6 / 1.027.3 / 2) 5.2 / 6.9

 K059

 450/350 32.2 132.3 / 137.5 / 3 (912.2 / 948.0 / 3) 2.9 / 2.9

 K061

 450/300 27.2 142.0 / 146.5 / 2 (979.1 / 1.010.1 / 2) 3.6 / 5.2

 K065

 450/300 32.4 137.8 / 143.1 / 1 (950.1 / 986.6 / 1) 6.9 / 6.9

 K066

 450/350 29.1 134.5 / 139.8 / 2 (927.3 / 963.9 / 2) 3.1 / 3.1

 K067

 500/300 38.6 132.4 / 137.0 / 2 (912.9 / 944.6 / 2) 3.8 / 5.2

 K068

 450/300 28.6 143.2 / 149.3 / 2 (987.3 / 1,029.4 / 2) 4.0 / 6.9

 K069

 450/350 30.3 134.1 / 139.4 / 3 (924.6 / 961.1 / 3) 4.0 / 6.9

 K070

 450/350 31.0 147.1 / 151.9 / 2 (1,014.2 / 1,047.3 / 2) 4.0 / 4.0

 K071

 450/350 33.5 134.9 / 140.0 / 3 (930.1 / 965.3 / 3) 3.1 / 3.3

 K072

 450/350 30.6 145.7 / 151.1 / 2 (1,004.6 / 1,041.8 / 2) 4.0 / 6.9

 K073

 450/350 33.8 141.6 / 146.6 / 2 (976.3 / 1.010.8 / 2) 3.8 / 4.0

 K074

 450/350 29.4 146.9 / 153.1 / 2 (1,012.8 / 1,055.6 / 2) 3.8 / 6.9

 K075

 450/350 26.2 145.4 / 152.9 / 3 (1,002.5 / 1,054.2 / 3) 5.2 / 8.7

 K076

 450/350 27.7 137.7 / 144.8 / 3 (949.4 / 998.4 / 3) 3.1 / 6.9

Example 4 - Effect of cobalt and chromium on mechanical strength and formability.

The alloys of Example 3 were heat treated in solution in a fluidized bed furnace, for 60 5 seconds, at the temperature indicated in Table 5. Figure 6 is a flow chart of the procedure of this Example 4. Subsequently, the alloys 25% cold rolled to 0.009 "(0.23mm) and then subjected to stabilization annealing of 400 to 500 ° C for 3 hours. After an additional cold reduction of 22% to 0.007" (0 , 18 mm), the samples were annealed and stabilized at temperatures of 300 to 400 ° C for 3 hours. Table 7 shows the properties of the representative conditions. Similar to Example 3, the alloys K068, K070 and K072 were of particular interest, which showed that the alloys containing Co, Cr or a combination of both achieved the highest levels of mechanical strength. Folding formability data indicated that K068 and K070 alloys, which both contained Co, had the best formability with greater mechanical strength. The limit of elasticity against conductivity was represented in Figure 7, and against the conformability by folding in Figure 8. The values of the 15 alloys K068, K070 and K072 are noteworthy.

5

10

fifteen

twenty

25

30

 Table 7: Properties of the SA-CR-stabilization-CR-stabilization procedure of Test 4 alloys

 Alloy

 Stabilizations% IACS YS / TS / EI ksi / ksi /% (MPa / MPa /%) 90 ° MBR / t

 K056

 450/300 29.1 147.4 / 152.4 / 2 (1,016.3 / 1,050.8 / 2) 5.7 / 8.6

 K057

 450/300 29.7 136.1 / 141.9 / 2 (938.4 / 978.4 / 2) 2.0 / 5.7

 K058

 450/300 25.6 146.7 / 153.3 / 1 (1,011.5 / 1,057.0 / 1) 2.0 / 8.6

 K065

 450/300 34.7 142.9 / 145.4 / 2 (1,011.5 / 1,002.5 / 2) 3.6 / 4.9

 K067

 500/300 38.4 137.4 / 141.7 / 3 (947.3 / 977.03) 2.9 / 5.7

 K068

 450/300 30.3 151.6 / 155.3 / 1 (1,045.2 / 1,070.8 / 1) 3.6 / 4.9

 K069

 450/300 29.7 139.4 / 145.7 / 1 (961.1 / 1,004.6 / 1) 2.9 / 8.6

 K070

 450/300 31.1 152.3 / 157.9 / 2 (1,050.1 / 1,088.7 / 2) 2.9 / 3.9

 K071

 450/300 34.8 143.8 / 147.6 / 2 (991.5 / 1.017.7 / 2) 2.9 / 3.9

 K072

 450/300 31.4 155.4 / 161.3 / 1 (1,071.4 / 1,112.1 / 1) 2.7 / 8.6

 K073

 450/300 34.7 147.2 / 150.9 / 2 (1,014.9 / 1,040.4 / 2) 2.7 / 3.9

 K074

 450/300 29.8 153.9 / 160.0 / 1 (1,061.1 / 1,103.2 / 1) 2.1 / 3.9

 K075

 450/300 26.5 151.4 / 158.2 / 2 (1,043.9 / 1,090.8 / 2) 2.0 / 11.0

 K076

 450/300 28.1 142.8 / 149.0 / 1 (984.6 / 1.027.3 / 1) 2.1 / 8.6

Example 5 - Nickel: cobalt ratio.

A series of 10 pound (4.5 kg) laboratory ingots were melted in a silica crucible with the compositions indicated in Table 8 and Durville was applied to steel molds that, after opening, were of approximately 4 ”x 4” x 1.75 ”(0.1 mx 0.1 mx 0.044 m). Figure 9 is a flow chart of the procedure of this Example 5. This group of alloys was based on K068 alloys, K070 and K072 of Table 5, where the global alloy level and the Ni / Co ratio were varied, while the stoichiometric ratio ((Ni + Co) / (Si-Cr / 5 was kept close to 4.2) )) After homogenizing them for two hours at 900 ° C, they were hot rolled in three passes at 1.1 ”(28 mm) (1.6" / 1.35 "/ 1.1") (41 mm / 34 mm / 28 mm), were reheated at 900 ° C for 10 minutes and additionally hot rolled in three passes at 0.50 "(13 mm) (0.9" / 0.7 "/ 0.5") (23 mm / 18 mm / 13 mm), followed by water quenching. das were then homogenized at 590 ° C for 6 hours, roughened and then milled to remove surface oxides that arose during hot rolling. The alloys were then cold rolled at 0.012 "(0.3 mm) and heat treated in solution in a fluidized bed furnace, for 60 seconds, at the temperature indicated in Table 8. The temperature was selected to maintain a relatively constant grain size The alloys were then subjected to a stabilization annealing of 450 to 500 ° C for 3 hours, designed to increase mechanical strength and conductivity, then the alloys were cold rolled 25% to 0.009 "(0.23 mm) and stabilized at 300 to 400 ° C for 4 hours. Table 9 shows the properties measured after the second stabilization annealing for a procedure with a first stabilization at 475 ° C and a second stabilization at 300 ° C. For the set of compositions with only Co (K077 to K085), the elastic limit values tended to increase with the elevation of the alloy content. For example, the K078 alloy, with a Ni + Co + Cr + Si value of 6.24, had an elasticity limit of 155 ksi (1,069 MPa), while the K084, with a Ni + Co + Cr value + If of 5.22, it had an elasticity limit of 139 ksi (958 MPa). A Ni / Co ratio of 3 to 4 provided better mechanical strength than a ratio of 5, when comparing alloy K077 (Ni / Co ratio of 3.62) and K078 (Ni / Co ratio of 3.83) with the K079 (Ni / Co ratio of 5.04), as well as when comparing the K080 alloy (Ni / Co ratio of 3.32) and the K081 (Ni / Co ratio of 3.93) with the K082 (Ni ratio / Co of 4.89). The representations of the elasticity limit versus the Ni / Co ratio in Figure 10 illustrate this, with the exception of K085, which had a higher Si level than K083 and K084. Alloys containing Co and Cr, K086 to K094, were not as sensitive to global alloy levels and the Ni / Co ratio as Alloys with Co only. Alloys with Co only (K095 to K097) also had properties comparable to those of other types of alloys.

 Table 8: Alloys of Example 5

 Alloy

 Composition analyzed% by weight Ni / Co Ni + Co + Cr + Si Ratio (Ni + Co) / (Si-Cr / 5) Annealing temperature in solution, ° C Grain size | jm

 K077

 Cu -3.84 Ni-1.06 Co -1.31 Yes 3.62 6.21 3.740 975 10.0

 K078

 Cu -3.98 Ni -1.04 Co -1.22 Yes 3.83 6.24 4,115 975 10.3

 K079

 Cu -4.28 Ni -0.85 Co -1.32 Yes 5.04 6.45 3.886 975 14.8

 K080

 Cu -3.49 Ni -1.05 Co -1.10 Yes 3.32 5.64 4,127 975 15.5

 K081

 Cu -3.77 Ni -0.96 Co -1.17 Yes 3.93 5.90 4,043 975 16.9

 K082

 Cu -3.86 Ni -0.79 Co -1.12 Yes 4.89 5.77 4,152 975 20.4

 K083

 Cu -3.22 Ni -1.05 Co -1.06 Yes 3.07 5.33 4,028 975 15.5

 K084

 Cu -3.33 Ni -0.89 Co -1.00 Yes 3.74 5.22 4,220 950 15.3

 K085

 Cu -3.59 Ni -0.75 Co -1.16 Yes 4.79 5.50 3.741 950 18.7

 K086

 Cu - 3.80 Ni -1.20 Co -1.46 Si - 0.57 Cr 3.17 7.03 3.715 975 10.9

 K087

 Cu -4.03 Ni -1.01 Co -1.37 Si -0.60 Cr 3.99 7.01 4.032 975 15.9

 K088

 Cu - 4.26 Ni - 0.82 Co -1.51 Si - 0.57 Cr 5.20 7.18 3.639 975 16.4

 K089

 Cu -3.50 Ni -1.11 Co -1.33 Si -0.58 Cr 3.15 6.52 3,797 975 10.5

 K090

 Cu - 3.75 Ni - 0.92 Co -1.25 Si - 0.55 Cr 4.08 6.47 4,096 975 16.3

 K091

 Cu - 3.97 Ni - 0.79 Co -1.42 Si - 0.56 Cr 5.03 6.74 3.639 975 16.7

 K092

 Cu - 3.25 Ni -1.01 Co -1.22 Si - 0.58 Cr 3.22 6.06 3.859 975 15.2

 K093

 Cu - 3.43 Ni - 0.86 Co -1.30 Si - 0.51 Cr 3.99 6.10 3,581 975 16.0

 K094

 Cu - 3.50 Ni - 0.73 Co -1.22 Si - 0.59 Cr 4.79 6.04 3.838 975 17.5

 K095

 Cu -4.97 Ni -1.36 Si -0.60 Cr 6.93 4.008 950 18.4

 K096

 Cu -4.63 Ni -1.35 Si -0.61 Cr 6.59 3.770 925 12.0

 K097

 Cu -4.20 Ni -1.18 Si -0.59 Cr 5.97 3.955 925 18.9

 Table 9: Properties of the SA-stabilization-CR-stabilization procedure of Example 5

 Alloy

 Stabilizations% IACS YS / TS / EI ksi / ksi /% (MPa / MPa /%) 90 ° MBR / t

 K077

 475/300 29.1 152.1 / 159.3 / 4 (1,048.7 / 1,098.3 / 4) 5.2 / 5.2

 K078

 475/300 29.7 155.5 / 162.3 / 4 (1,072.1 / 1,119.0 / 4) 5.2 / 5.2

 K079

 475/300 30.7 143.7 / 150.1 / 4 (990.8 / 1.034.9 / 4)

 K080

 475/300 31.2 142.4 / 147.9 / 3 (981.8 / 1.019.7 / 3) 5.2 / 3.6

 K081

 475/300 30.7 144.2 / 148.3 / 3 (994.2 / 1.022.5 / 3) 4.0 / 6.1

 K082

 475/300 32.2 137.7 / 142.7 / 2 (949.4 / 983.9 / 2)

 K083

 475/300 31.1 140.0 / 145.8 / 3 (965.3 / 1,005.3 / 3) 5.2 / 5.2

 K084

 475/300 32.1 138.9 / 145.6 / 3 (957.7 / 1,003.9 / 3)

 K085

 475/300 31.8 140.4 / 146.3 / 2 (968.0 / 1,008.7 / 2)

 K086

 475/300 30.1 151.6 / 157.9 / 4 (1,045.2 / 1,088.7 / 4) 5.2 / 6.1

 K087

 475/300 30.5 149.4 / 153.6 / 3 (1,030.1 / 1,059.0 / 3) 5.2 / 3.6

 K088

 475/300 30.4 152.2 / 159.3 / 4 (1,049.4 / 1,098.3 / 4) 5.2 / 5.2

 K089

 475/300 30.3 149.0 / 155.6 / 3 (1,027.3 / 1,072.8 / 3) 4.0 / 5.2

 K090

 475/300 31.3 151.9 / 157.4 / 3 (1,047.3 / 1,085.2 / 3) 5.2 / 3.8

 K091

 475/300 30.7 149.5 / 154.5 / 3 (1,030.8 / 1,065.2 / 3) 5.2 / 6.1

 K092

 475/300 30.8 146.5 / 152.1 / 3 (1,010.1 / 1,048.7 / 3) 4.0 / 5.2

 K093

 475/300 30.3 147.2 / 153.4 / 4 (1,014.9 / 1,057.7 / 4) 5.2 / 5.2

 K094

 475/300 31.2 148.1 / 154.4 / 2 (1,021.1 / 1,064.6 / 2) 4.0 / 3.8

 K095

 475/300 30.7 150.2 / 159.1 / 3 (1,035.6 / 1,097.0 / 3) 3.8 / 6.1

 K096

 475/300 32.1 153.3 / 160.6 / 4 (1,057.0 / 1,107.3 / 4) 4.0 / 6.1

 K097

 475/300 31.9 148.7 / 155.5 / 3 (1,025.3 / 1,072.1 / 3) 3.8 / 5.2

The alloys in Table 8 were heat treated in solution in a fluidized bed furnace, for 60 seconds, at the temperature indicated in Table 8. Subsequently, the alloys were cold rolled 25% at 0.009 ”(0.23 mm ) and then underwent a stabilization annealing of 450 to 500 ° C for 3 hours. After an additional cold reduction of 22% to 0.007 "(0.18 mm), the samples were annealed and stabilized at temperatures of 300 to 400 ° C for 3 hours. Table 10 shows the properties of the samples provided in a first and second stabilization at 450 ° C and 300 ° C, respectively. Alloys with Co only showed a sensitivity to global alloy levels with this scheme that has not been found in alloys containing Cr. Alloys with Co only with an elasticity limit of 10 150 ksi (1,034 MPa) and higher were the K077 and the K078, while all the alloys containing Cr

reached or approached that level of elasticity limit. The mechanical-folding resistance properties for this procedure were quite similar to those in Table 9.

 Table 10: Properties of the SA-CR-stabilization-CR-stabilization procedure of Example 5

 Alloy

 Stabilizations% IACS YS / TS / EI ksi / ksi /% (MPa / MPa /%) 90 ° MBR / t

 K077

 450/300 29.1 152.8 / 160.2 / 2 (1,053.5 / 1,104.5 / 2) 3.7 / 4.3

 K078

 450/300 30.1 149.7 / 157.7 / 4 (1,032.1 / 1,087.3 / 4) 4.0 / 4.9

 K079

 450/300 35.2 133.4 / 140.3 / 2 (919.8 / 967.3 / 2)

 K080

 450/300 32.2 133.1 / 139.6 / 2 (917.7 / 962.5 / 2)

 K081

 450/300 32.2 133.0 / 138.8 / 2 (917.0 / 957.0 / 2)

 K082

 450/300 44.9 100.7 / 112.9 / 3 (694.3 / 778.4 / 3)

 K083

 450/300 30.2 140.7 / 145.8 / 3 (970.1 / 1,005.3 / 3)

 K084

 450/300 $ 1.8 141.7 / 146.7 / 3 (977.0 / 1.011.5 / 3) 4.0 / 5.1

 K085

 450/300 31.2 141.4 / 146.7 / 2 (974.9 / 1.011.5 / 2)

 K086

 450/300 30.3 150.8 / 156.6 / 2 (1,039.7 / 1,079.7 / 2) 4.9 / 6.7

 K087

 450/300 30.2 153.4 / 158.7 / 2 (1,057.7 / 1,094.2 / 2) 4.6 / 4.9

 K088

 450/300 28.6 153.7 / 159.4 / 2 (1,059.7 / 1,099.0 / 2) 3.7 / 6.7

 K089

 450/300 29.8 148.9 / 155.4 / 1 (1,026.6 / 1,071.4 / 1) 4.6 / 6.7

 K090

 450/300 29.9 151.3 / 155.9 / 3 (1043.2 / 1,074.9 / 3) 4.6 / 4.3

 K091

 450/300 30.0 152.4 / 159.5 / 1 (1,050.8 / 1,099.7 / 1) 4.0 / 6.7

 K092

 450/300 32.5 149.6 / 156.4 / 3 (1,031.5 / 1,078.3 / 3) 4.3 / 6.7

 K093

 450/300 30.3 147.1 / 152.7 / 2 (1,014.2 / 1,052.8 / 2) 4.6 / 6.7

 K094

 450/300 29.9 160.4 / 156.9 / 2 (1,105.9 / 1,081.8 / 2) 4.3 / 4.9

 K095

 450/300 30.0 155.9 / 165.3 / 2 (1,074.9 / 1,139.7 / 2) 4.0 / 6.7

 K096

 450/300 31.8 157.5 / 165.4 / 3 (1,085.9 / 1,140.4 / 3) 4.0 / 6.7

 K097

 450/300 32.0 155.1 / 161.6 / 3 (1,069.4 / 1,114.2 / 3) 4.3 / 4.9

Example 6 - Nickel: cobalt ratio.

Laboratory ingots were melted in a graphite crucible with the compositions indicated in Table 11, and Tamman was applied to steel molds which, after opening, were 4.33 "X 2.17" X 1.02 "(110 5 mm X 55 mm X 26 mm). Figure 11 is a flow chart of the procedure of this Example 6. For a desired Si content of 1% and a Cr content of 0.5% , with an alloy containing Co and another that did not contain Co, the Ni content was adjusted in order to maintain a stoichiometric ratio ((Ni + Co) / (Si-Cr / 5)) close to 4.2. if homogenized for two hours at 900 ° C, they were hot rolled at 0.472 "(12 mm), and then reheated after each pass at 900 ° C for 10 minutes. After the last pass, the 10 bar was heated in water. After roughing and milling at 0.394 "(10 mm) in order to remove surface oxide, the alloys were cold rolled to 0.0106" (0.27 mm) and heat treated in solution in a fluidized bed furnace during the time and temperature indicated in Table 11. The time and temperature were selected to achieve grain sizes below 20 pm. The alloys were then subjected to a stabilization annealing of 450 to 500 ° C for 3 hours, designed to increase mechanical strength and conductivity. The alloys were then cold rolled 25% at 0.0079 "(0.2 mm) and stabilized at 300 or 400 ° C for 3 hours. Table 12 shows the properties measured after the second stabilization annealing. The conformability was measured by means of a V-groove block. The data indicates that both alloys were able to reach an elasticity limit of 135 ksi (931 MPa), but the BS variant containing Co showed a better resistance to softening. , which can be observed with the increase in stabilization annealing temperature 20. The slightly better folding in an unfavorable sense of the BS variant is presumably due to a slightly smaller grain size after solution annealing.

 Table 11: Alloys of Example 6,% by weight

 Alloy

 Ni Co Cr Si Mg Ratio (Ni + Co) / (Si-Cr / 5) Ni / Co SA conditions Grain size, pm

 BR

 3.59 0.48 1.00 3.97 CO 915 ° C -1 minute 10-15

 BS

 3.18 0.47 0.49 0.97 4.19 6.77 950 ° C -1 minute 5-10

 Table 12 - Properties of the SA-stabilization-CR-stabilization procedure of Example 6

 Alloy

 1.AA 2.AA 300 ° C / 3 h 2.AA 400 ° C / 3 h

 Temp. ° C

 YS, ksi (MPa) TS, ksi (MPa) A10%% IACS 90 ° MINBR / t YS, ksi (MPa) TS, ksi (MPa) A10%% IACS 90 ° MINBR / t

 BR

 450 135.8 (936.3) 144.2 (994.2) 3.7 32.5 4.0 / 5.0 118.2 (815.0) 129.5 (892.9) 6.5 37 ,one -/-

5

10

fifteen

twenty

25

30

 475 133.9 (923.2) 141.8 (977.7) 3.7 35.1 4.0 / 6.0 124.0 (855.0) 132.9 (916.3) 7.9 38 ,5 -/-

 500

 117.3 (808.8) 123.6 (852.2) 5 37.1 4.0 / 4.0 100.1 (690.2) 108.8 (750.1) 11 41.6 - / -

 BS

 450 135.8 (936.3) 142.6 (983.2) 1.6 31.7 4.0 / 4.0 128.2 (883.9) 137.2 (946.0) 3.7 33 , 5 3.5 / 4.0

 475

 132.7 (914.9) 138.4 (954.2) 1.7 34.6 5.0 / 5.5 126.5 (872.2) 136.2 (939.1) 2.3 38, 3 4.0 / 4.5

 500

 127.3 (877.7) 134.7 (928.7) 4.8 37.4 4.0 / 5.0 119.4 (823.2) 127.8 (881.2) 6 41.2 - / -

Example 7 - Relationship (Ni + Co) / (Si-Cr / 5).

A group of alloys was cast and treated using, once again, the basic compositions of alloys K068 (Co only), K070 (Co and Cr) and K072 (Cr only) of Table 5, but in this case with a gradual decrease in Si levels, thereby increasing the stoichiometric ratio (Ni + Co) / (Si-Cr / 5) above the range of 3.6 to 4.2 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 10-pound (4.5 kg) laboratory ingots were melted in a silica crucible with the compositions indicated in Table 11 and Durville was applied to steel molds which, after opening, were of approximately 4 "x 4" x 1.75 "(0.1 mx 0.1 mx 0.044 m). Alloys K143 to K146 are variants of K072, K160 to K163 are variants of K070, and K164 to K167 they are variants of the K068. Figure 12 is a flow chart of the procedure of this Example 7. After homogenizing them for two hours at 900 ° C, they were hot rolled in three passes at 1.1 "(28 mm) (1 , 6 "/ 1.35" / 1.1 "), (41 mm / 34 mm / 28 mm), were reheated at 900 ° C for 10 minutes, and additionally hot rolled in three passes at 0.50" (13 mm) (0.9 "/ 0.7" / 0.5 ") (23 mm / 18 mm / 13 mm), followed by water quenching. Then, the tempered plates were homogenized at 590 ° C for 6 hours, they were roughened and then milled to remove the oxides s surfaces emerged during hot rolling. Then, the alloys were cold rolled at 0.012 "(0.3 mm) and heat treated in solution in a fluidized bed furnace, for 60 seconds, at the temperatures indicated in Table 13. The temperature was selected to maintain a relatively constant grain size. The alloys were then cold rolled 25% at 0.009 "(0.23 mm) and stabilized at 450, 475 and 500 ° C for 3 hours. Table 14 shows the properties after each stabilization temperature for the alloys of the current example, as well as for the alloys K068, K070, K072, K078, K087 and K089. For each type of alloy, the elasticity limit decreased as the stoichiometric ratio increased above approximately 4.5, and was below 120 ksi (827 MPa) for 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 Co and Cr alloys, conductivity decreased as the stoichiometric ratio increased above 4.5, while for alloys with Co and Cr there is no clear relationship between stoichiometry and conductivity. This is shown graphically in Figures 16 to 18. Based on these data, it is evident that the best elastic-conductivity limit properties occurred when the stoichiometric ratio remained between 3.5 and 5.0.

 Table 13: Alloys of Example 7

 Alloy

 Ni Co Cr Si Mg Ratio (Ni + Co) / (Si-Cr / 5) Ni / Co Temperature of SA

 K143

 4.61 0.519 1.11 0.099 4.582 950

 K144

 4.63 0.503 0.828 0.074 6.365 950

 K145

 4.59 0.607 0.91 0.085 5.820 950

 K146

 4.55 0.576 0.803 0.093 6.615 950

 K160

 3.84 1.2 0.52 1.19 4,641 3.20 975

 K161

 3.8 1.18 0.515 1.1 4.995 3.22 975

 K162

 3.83 1.2 0.513 1.03 5.424 3.19 975

 K163

 3.84 1.21 0.556 0.938 6.108 3.17 975

 K164

 3.74 1.17 1.05 0.104 4.676 3.20 975

 K165

 3.9 1.23 1.01 0.116 5.079 3.17 975

 K166

 3.87 1.23 0.918 0.12 5.558 3.15 975

 K167

 3.9 1.24 0.83 0.085 6.193 3.15 975

 Table 14: Properties after solution annealing, 25% cold rolling and stabilization of Example 7

 Alloy

 Stabilization at 450 ° C Stabilization at 475 ° C Stabilization at 500 ° C

 YS ksi (MPa)

 % IACS Folded at 90 ° YS ksi (MPa)% IACS Folded at 90 ° YS ksi (MPa)% IACS Folded at 90 °

 K143

 138.9 (957.7) 31.2 2.9 / 2.0 135.8 (936.3) 33.7 2.0 / 2.7 126.3 (870.8) 35.8 2.0 / 2.2

 K144

 118.1 (814.3) 27.5 1.8 / 2.2 125.6 (866.0) 30.8 1.3 / 1.1 121.3 (836.3) 33.1 2.2 / 1.3

 K145

 120.8 (832.9) 27.3 2.0 / 1.3 127.5 (879.1) 30.3 2.2 / 1.3 123.5 (851.6) 32.6 2.2 / 1.8

 K146

 113.4 (781.9) 26.8 1.8 / 1.1 121.7 (839.1) 30.4 2.2 / 2.0 116.8 (805.3) 32.2 1.3 / 1.6

 K160

 127.4 (878.4) 29.5 2.0 / 3.1 133.8 (922.6) 34.0 2.4 / 1.6 122.6 (845.3) 39.3 1.8 / 1.8

 K161

 127.4 (878.4) 29.4 2.4 / 1.1 131.3 (905.3) 33.0 2.2 / 1.6 123.5 (851.6) 35.7 1.8 / 0.7

 K162

 122.4 (843.9) 33.4 1.3 / 1.3 120.7 (832.2) 34.4 2.4 / 1.3 116.5 (803.2) 35.9 1.6 / 1.3

 K163

 120.7 (832.2) 29.8 1.3 / 1.1 119.4 (823.2) 32.0 1.6 / 1.1 111.1 (766.1) 34.2 1.6 / 1.1

 K164

 126.6 (872.9) 29.9 2.4 / 1.6 132.6 (914.2) 3.3.7 2.4 / 2.0 125.8 (867.4) 36.7 2 , 0 / 2.9

 K165

 118.9 (819.8) 29.6 2.2 / 1.6 124.0 (855.0) 32.9 2.2 / 2.4 119.5 (823.9) 35.4 1.6 / 1.8

 K166

 116.6 (803.9) 27.9 2.0 / 1.3 120.4 (830.1) 30.4 2.9 / 1.1 117.7 (811.5) 32.5 2.0 / 1.8

 K167

 111.6 (769.5) 25.7 2.0 / 1.6 114.5 (789.4) 27.4 1.6 / 1.3 113.4 (781.9) 29.3 1.3 / 0.2

 K068

 131.9 (909.4) 29.3 2.2 / 2.8 131.7 (908.0) 33.5 2.2 / 2.2

 K070

 134.7 (928.7) 29.7 2.2 / 1.6 129.7 (894.3) 33.6 1.7 / 1.6

 K072

 133.3 (919.1) 29.9 1.7 / 1.7 130.0 (896.3) 33.2 1.6 / 2.2

 K078

 125.3 (863.9) 30.8 - - 133.3 (919.1) 31.9 2.2 / 1.6 125.7 (866.7) 36.3 - -

 K087

 133.4 (919.8) 29.0 - - 136.9 (943.9) 30.7 2.2 / 1.6 124.1 (855.6) 37.7 - -

 K089

 136.2 (939.1) 29.9 - - 135.0 (930.8) 30.6 - - 131.5 (906.7) 34.4 - -

Example 8 - Relationship (Ni + Co) / (Si-Cr / 5).

A series of 10-pound (4.5 kg) laboratory ingots were melted in a silica crucible with the compositions 5 indicated in Table 15 and Durville was applied to steel molds which, after opening, were approximately 4 "x 4" x 1.75 "(0.1 mx 0.1 mx 0.044 m). Figure 19 is a flow chart of the procedure of this Example 8. After homogenizing them for two hours at 900 ° C, they were hot rolled in three passes at 1.1 "(28 mm) (1.6" / 1, 35 "/ 1.1") (41 mm / 34 mm / 28 mm), reheated to 900 ° C for 10 minutes, and then hot rolled in three passes at 0.50 "(13 mm) (0, 9 "/ 0.7" / 0.5 ") (23 mm / 10 18 mm / 13 mm), followed by water quenching. Tempered plates were homogenized at 590 ° C for 6

hours, they were roughened and then milled to remove surface oxides that arose during hot rolling. The alloys were then cold rolled at 0.012 "(0.3 mm) and heat treated in solution in a fluidized bed furnace, for 60 seconds, at 950 ° C. The grain size varied from 6 to 12 pm. The alloys were then subjected to a stabilization annealing of 450 or 475 ° C for 3 hours, designed to increase mechanical strength and conductivity. Then, the alloys were cold rolled 25% to 0.009 "(0.18 mm) and

they stabilized at 300 ° C for 4 hours. Table 16 shows the properties measured after the second stabilization annealing.

Table 17 includes the measured properties after the samples were heat treated in solution in a fluidized bed furnace for 60 seconds at 950 ° C, 25% cold rolled at 0.009 ”(0.23 mm), given to them. 5 would give a stabilization annealing at 475 ° C for 3 hours, 22% cold rolling at 0.007 ”(0.18 mm), and a final annealing of 300 ° C for 3 hours. The results show the viability of a range of compositions with 1.0 to 1.2% Si, with a Ni / Co ratio of 4 and a stoichiometric ratio ((Ni + Co) / (Si-Cr / 5)) of 3.5 to 5.0, This is shown graphically in Figures 20 and 21, which represent the conductivity data and the elasticity limit of Table 17, versus the stoichiometric relationship. These graphs show limits of 10 elasticity of 140 ksi (965 MPa) or higher, combined with conductivities of 25% IACS or higher, which are obtained by this procedure when the ratio is between 3.0 and 5.0. It was not found that Cr significantly influenced the properties of the alloys in this example.

Stress relaxation tests were performed on samples of K188 and K205 alloys that were cold rolled at 0.012 "(0.3 mm) from a hot rolled milled plate, annealed at 950 ° C for 60 seconds, 25% cold rolled at 0.009 "(0.23 mm), and annealed and stabilized at 475 ° C for 3 hours. Stress relaxation tests were performed at 150 ° C for 3,000 hours on samples of longitudinal and transverse orientation The results in Table 18 show that both alloys had excellent resistance to stress relaxation, above 85% of the remaining tension after 1,000 hours at 150 ° C, regardless of Cr or of the orientation of the sample.

 Table 15: Alloys of Example 8

 Alloy

 Composition analyzed,% by weight Ni / Co Stoichiometric ratio Grain size, pm

 K188

 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

 K190

 Cu - 3.22 Ni - 0.70 Co -1.28 Si - 0.31 Cr - 0.036 Mg 4.59 3.22 8.5

 K191

 Cu - 3.22 Ni - 0.70 Co -1.05 Si - 0.53 Cr - 0.064 Mg 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 - 3.21 Ni - 0.90 Co -1.05 Si - 0.34 Cr - 0.117 Mg 3.56 4.16 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 - 0.88 Co - 0.81 Si - 0.52 Cr - 0.070 Mg 3.71 5.72 7.1

 K196

 Cu - 3.19 Ni - 0.89 Co -1.28 Si - 0.57 Cr - 0.111 Mg 3.60 3.49 7.7

 K197

 Cu - 3.61 Ni - 0.70 Co -1.06 Si - 0.36 Cr - 0.067 Mg 5.14 4.36 10.7

 K198

 Cu - 3.60 Ni - 0.70 Co -1.28 Si - 0.39 Cr - 0.077 Mg 5.13 3.58 8.7

 K199

 Cu - 3.60 Ni - 0.70 Co -1.06 Si - 0.60 Cr - 0.076 Mg 5.13 4.58 9.3

 K200

 Cu - 3.60 Ni - 0.70 Co -1.28 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 Ni - 0.90 Co -1.27 Si - 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 Cr - 0.076 Mg 4.04 4.77 6.1

 K204

 Cu - 3.58 Ni - 0.88 Co -1.27 Si - 0.56 Cr - 0.075 Mg 4.09 3.85 5.9

 K205

 Cu - 3.73 Ni - 0.91 Co -1.13 Si - 0.082 Mg 4.09 4.11 12.1

 K206

 Cu - 3.53 Ni - 0.81 Co -1.02 Si - 0.080 Mg 4.36 4.25 12.2

 K207

 Cu - 3.53 Ni - 0.78 Co -1.25 Si - 0.055 Mg 4.55 3.44 9.9

 K208

 Cu - 3.57 Ni -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 - 0.085 Mg 3.47 3.65 7.4

 K210

 Cu - 3.94 Ni - 0.82 Co -1.06 Si - 0.149 Mg 4.78 4.49 9.5

 K211

 Cu - 3.97 Ni - 0.80 Co -1.24 Si - 0.065 Mg 4.97 3.85 11.5

 K212

 Cu - 3.95 Ni - 0.99 Co -1.04 Si - 0.100 Mg 4.01 4.75 10.2

 K213

 Cu - 3.97 Ni - 0.99 Co -1.22 Si - 0.079 Mg 4.01 4.07 10.2

 Table 16 - Properties of the SA-stabilization-CR-stabilization procedure of Example 8

 Alloy

 Stabilizations% IACS YS / TS / EI ksi / ksi /% (MPa / MPa /%) 90 ° MBR / t

 K188

 450/300 29.3 149.5 / 156.1 / 2 (1,030.8 / 1,076.3 / 2) 3.3 / 5.2

 K189

 475/300 33.6 147.3 / 153.8 / 2 (1,015.6 / 1,060.4 / 2) 4.0 / 4.0

 K204

 450/300 29.7 149.6 / 155.1 / 2 (1,031.5 / 1,069.4 / 2) 4.0 / 5.2

 K205

 475/300 34.2 149.8 / 155.7 / 2 (1,032.8 / 1,073.5 / 2) 4.0 / 5.2

 K206

 475/300 35.0 147.9 / 153.9 / 2 (1,019.7 / 1,061.1 / 2) 4.0 / 5.3

 K213

 475/300 34.2 150.8 / 157.4 / 2 (1,039.7 / 1,085.2 / 2) 5.2 / 5.2

 Table 17: Properties of the SA-CR-stabilization-CR-stabilization procedure of Example 8

 Alloy

 Stabilizations% IACS YS / TS / EI ksi / ksi /% (MPa / MPa /%) 90 ° MBR / t

 K188

 475/300 35.1 145.7 / 152.4 / 3 (1,004.6 / 1,050.8 / 3) 2.0 / 4.9

 K189

 475/300 34.7 146.1 / 152.6 / 2 (1,007.3 / 1,052.1 / 2) 2.6 / 5.7

 K190

 475/300 28.0 139.2 / 148.5 / 4 (959.7 / 1.023.9 / 4) 2.9 / 5.1

 K191

 475/300 37.2 143.7 / 149.9 / 3 (990.8 / 1.033.5 / 3) 3.4 / 6.7

 K192

 475/300 28.1 139.7 / 146.4 / 2 (963.2 / 1,009.4 / 2) 2.6 / 6.7

 K193

 475/300 36.2 143.6 / 149.3 / 3 (990.1 / 1.029.4 / 3) 2.9 / 5.1

 K194

 475/300 29.1 138.7 / 146.1 / 3 (956.3 / 1,007.3 / 3) 2.6 / 6.7

 Kt95

 475/300 35.5 130.7 / 134.7 / 4 (901.1 / 928.7 / 4) 2.0 / 3.4

 K196

 475/300 30.2 143.4 / 149.5 / 2 (988.7 / 1,030.8 / 2) 2.6 / 9.0

 K197

 475/300 35.4 145.3 / 152.0 / 2 (1,001.8 / 1,048.0 / 2) 3.1 / 6.7

 K198

 475/300 31.7 148.2 / 155.7 / 3 (1,021.8 / 1,073.5 / 3) 2.9 / 6.7

 K199

 475/300 35.5 147.8 / 154.4 / 3 (1,019.0 / 1,064.5 / 3) 2.9 / 9.0

 K200

 475/300 33.7 146.3 / 152.9 / 3 (1,008.7 / 1,054.2 / 3) 3.4 / 6.7

 K201

 475/300 36.8 145.2 / 150.0 / 2 (1,001.1 / 1,034.2 / 2) 2.9 / 6.7

 K202

 475/300 33.5 146.1 / 152.8 / 3 (1,007.3 / 1,053.5 / 3) 2.6 / 5.1

 K203

 475/300 34.4 147.4 / 153.6 / 2 (1,016.3 / 1,059.0 / 2) 3.6 / 5.7

5

10

fifteen

twenty

25

 K204

 475/300 33.9 150.3 / 156.8 / 3 (1,036.3 / 1,081.1 / 3) 2.9 / 6.7

 K205

 475/300 35.3 147.0 / 152.8 / 2 (1,013.5 / 1,053.5 / 2) 2.9 / 5.7

 K206

 475/300 35.8 146.9 / 153.7 / 3 (1,012.8 / 1,059.7 / 3) 2.4 / 6.7

 K207

 475/300 29.7 143.3 / 150.3 / 2 (988.0 / 1,036.3 / 2) 2.6 / 6.7

 K206

 475/300 36.2 142.5 / 148.1 / 3 (982.5 / 1.021.1 / 3) 2.9 / 6.7

 K209

 475/300 32.2 145.5 / 152.1 / 3 (1,003.2 / 1,048.7 / 3) 2.6 / 6.7

 K210

 475/300 34.1 148.6 / 154.1 / 5 (1,024.6 / 1,062.5 / 5) 2.9 / 6.7

 K211

 475/300 33.8 144.7 / 152.1 / 2 (997.7 / 1,048.7 / 2) 3.1 / 5.1

 K212

 475/300 34.5 140.6 / 145.4 / 3 (969.4 / 1,002.5 / 3) 2.9 / 5.7

 K213

 475/300 35.0 148.4 / 154.4 / 2 (1,023.2 / 1,064.5 / 2) 3.6 / 6.7

Table 18: Stress relaxation data for 25% cold rolled samples stabilized at 475 ° C for 3 hours of Example 8

 Alloy

 Limit of elasticity ksi (MPa) Longitudinal Transversal

 (percentage tension remaining)

 (percentage tension remaining)

 1,000 h

 3,000 h 1,000 h 3,000 h

 K188 (Cr)

 136.4 (940.4) 89.9 87.9 88.2 85.2

 K205 (without Cr)

 132.2 (911.5) 92.0 90.4 91.6 89.6

Example 9 - Effect of Cr.

A series of 10-pound (4.5 kg) laboratory ingots were melted in a silica crucible with the compositions indicated in Table 19 and Durville was applied to steel molds that, after opening, were of approximately 4 ”x 4” x 1.75 ”(0.1 mx 0.1 mx 0.044 m). Figure 22 is a flow chart of the procedure in this Example 9. Then, the ingots were machined to have edges conical, as schematically illustrated in Figure 23, to create a higher state of tensile tension at the edges.This condition is more prone to cracking of the edges than that of standard flat edges, and therefore more sensitive to Alloy additions, in this case of Cr. The alloys were homogenized for two hours at 900 ° C and rolled in two passes at 1.12 "(28.4 mm) (1.4" / 1.12 ") ( 35.6 mm / 28.4 mm) and then tempered in water After the fissure examination, the bars were reheated to 900 ° C for two hours and laminated in three passes at 0.50 "(13 mm) (0.9" / 0.7 "/ 0.5") (23 mm / 18 mm / 13 mm), followed by water quenching . It was found that without Cr, large cracks emerged in the K224 alloy during the first hot rolling stages, which were enlarged during the remaining passes. In none of the alloys containing Cr did large cracks arise during hot rolling. A few alloys showed small cracks after the initial passes, which is believed to have been due to casting defects, but these were not enlarged during subsequent passes. The effect of Cr was the same regardless of the Cr level from 0.11% to 0.55%. Examples of the conditions of the edges of the alloys K224 and K225 after hot rolling are shown in Figures 24 and 25. The addition of Cr, even in a small amount, reduced cracking in the production of the plant, thereby improving performance after hot rolling and coil milling. The data of the bars cast in the plant (i.e. cast bars in the form of casts of the test product), whose compositions are indicated in Table 20, show the beneficial effect of Cr in the prevention of cracks by hot rolling and, Therefore, they improve performance. Table 21 indicates the standardized yield of the laundry plant (CPY) of six bars containing Cr and four bars that did not contain Cr, where the normalized CPY was obtained as follows: First, the individualized CPY was calculated as the relationship between the weight of the milling in coil and the weight of the casting bar. Secondly, the bar with the highest CPY, in this case RN0334101, was assigned a standard CPY of 100%. In third

instead, the standard CPY of all other bars was calculated, dividing the CPY of each bar by the CPY of RN033410. The standard CPY of bars without Cr was 48-82% compared to 82-100% for bars containing Cr

It is desirable to limit the Cr level due to the abrasiveness of Cr silicides, which is shown in Figure 26.

5 Figure 26A shows the wear on a steel ball of a tool that slid by 3,000 linear inches (76 m) (1,500 inches (38 m) on each side of the band), under a load of 100 g above the surface of the strip, with pig fat oil as a lubricant, of a sample without Cr (RN033407) that was annealed in solution at the plant at 975 ° C, 25% cold rolled and then stabilized at 450 ° C and was cleaned in sulfuric acid; while Figure 26B had a similar condition using a sample of an alloy containing Cr 10 (RN834062). The polished appearance of the ball shown in Fig. 26 shows that the alloy containing Cr

caused much more wear, which led to a significantly larger volume of ball material being removed. This is seen in Fig. 26 as a much larger wear mark for the alloy containing Cr. The larger wear mark suggests that during the stamping of the sheet of the alloy into pieces, great wear 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 1.20 0.035

 K228

 3.51 0.85 0.48 1.21 0.040

 K229

 3.39 0.85 0.55 1.20 0.043

fifteen

 Table 20: Compositions of the plant cast bars of Example 9

 Bar

 Ni Co Cr Si Mg

 RN032031

 3.71 0.75 - 1.09 0.12

 RN032038

 RN033407

 3.66 0.88 - 1.07 0.106

 RN033408

 RN033409

 3.83 0.89 0.45 1.22 0.138

 AN033410

 AN834059

 3.24 0.758 0.425 1.02 0.094

 RN834060

 RN834061

 3.45 0.74 0.44 1.14 0.076

 RN834062

 Table 21: Milling data for plant cast bars of Example 9

 Bar

 Type CPY% (normalized)

 RN032037

 Without Cr 75.2%

 RN032038

 Without Cr 48.1%

 RN033407

 Without Cr 76.0%

 RN033408

 Without Cr 82.3%

 AN033409

 Cr 95.6%

 RN033410

 100% Cr

 RN834059

 Cr 92.1%

 RN834060

 Cr 90.1%

 RN834061

 Cr 87.7%

 RN834062

 Cr 82.0%

In a single casting operation three bars were produced with the composition shown in Table 21a. Table 21b provides the yield of the bar casting plant, which was standardized similarly to the data in Table 21 where RN033410 was considered 100%. The CPY of the bars with a low Cr 5 content was favorably compared with the bars containing Cr of Table 21. This is believed to be due to the reduction of Cr cracking during hot rolling even at these low levels . RN037969 had a normalized% of CPY above 100, due to the fact that the performance of this bar was greater than that of RN033410 in the previous example.

 Table 21a: Analyzed compositions of bars with low Cr content and treated 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 content 89.8%

 RN037971

 Low Cr content 68.4%

10

Example 10 - Effect of Cr and Mn.

A series of 10 pound (4.5 kg) laboratory ingots were melted in a silica crucible with the compositions indicated in Table 22 and Durville was applied to steel molds that, after opening, were of approximately 4 "x 4" x 1.75 "(0.1 mx 0.1 mx 0.044 m). Figure 27 is a flow chart of the procedure of this Example 10. The K259 alloy contained a Cr level lower than that of the alloys of Example 9 to investigate the lower limits of the beneficial effect of Cr on hot rolling, alloys K251, K254 and K260 contained low levels of Mn to determine whether Mn affected the hot rolling of the alloy of this invention The ingots were then machined to have tapered edges, as schematically depicted in Fig. 23, to create a higher tensile state of tension at the edges.The alloys were homogenized for two hours at 900 ° C, and the they mined in two passes at 1.12 ”(28.4 mm) (1.4" / 1.12 ") (35.6 mm / 28.4 mm) and then tempered in water. After the fissure examination, the bars were reheated at 900 ° C for two hours, and laminated in three passes at 0.50 "(13 mm) (0.9" / 0.7 "/ 0.5") (23 mm / 18 mm / 13 mm), followed by water quenching. The K259 alloy, with 0.058% Cr, was hot rolled without cracking at the edges. In alloys containing Mn,

along with the K261 (without Cr or Mn) large fissures appeared at the edges. Therefore, an addition of Cr close to 0.05%, with a preferred range of 0.025 to 0.1% Cr, appeared to be appropriate for balancing hot rolling and abrasive particle formation leading to wear of the tool.

The tempered bars were homogenized at 590 ° C for 6 hours, roughened and then milled to eliminate surface oxides that arose during hot rolling. The alloys were then cold rolled at 0.012 "(0.3 mm) and heat treated in solution in a fluidized bed furnace, for 60 seconds, at 950 ° C. The alloys were then subjected to a stabilization annealing of 475 ° C for 3 hours, designed to increase mechanical strength and conductivity. The alloys were then cold rolled 25% to 0.009 "(0.23 mm) and stabilized at 300 ° C for 3 hours. Alternatively, after heat treatment in solution, the alloys were cold rolled 25% at 0.009 "(0.23 mm), given an annealing stabilization at 475 ° C for 3 hours, cold rolled at 22 % at 0.007 "(0.18 mm), and were given a final anneal of 300 ° C for 3 hours. Table 23 shows the properties after final stabilization for both procedure routes. For both procedures, with low levels of Cr and Mn or with none of them, an exceptionally good combination of properties was achieved, with an elasticity limit of 150 ksi 15 (1,034 MPa) and at least 31% IACS. Figures 28 and 29 are represented conductivity and elasticity limit

versus the stoichiometric ratio ((Ni + Co) / (Si-Cr / 5)), together with the data in Example 8, to show the unusually good properties achieved when the ratio remained between 3.0 and 5.0.

 Table 22: Low Cr and Mn Alloys of Example 10

 Alloy

 Ni Co Si Mg Cr Mn Ratio *

 K251

 3.64 0.84 1.16 0.058 - - 0.026 3.862

 K254

 3.73 0.90 1.16 0.044 - - 0.061 3.991

 K259

 3.78 0.56 1.14 0.073 0.058 0.004 3.846

 K260

 3.15 0.94 1.15 0.065 <0.001 0.048 4.078

 K261

 3.79 0.95 1.16 0.054 <: 0.001 0.004 4.086

* Ratio = (Ni + Co) / (Si-Cr / 5)

 Table 23: Properties for Example 10

 Alloy

 Procedure SA-stabilization-CR-stabilization Procedure SA-CR-stabilization-CR-stabilization

 % IACS

 YS / TS / EI ksi / ksi /% (MPa / MPa /%) 90 ° MBR / t% IACS YS / TS / EI ksi / ksi /% (MPa / MPa /%) 90 ° MBR / t

 K251

 31.0 149.9 / 156.5 / 1 (1,033.5 / 1,079.0 / 1) 4.0 / 5.2 32.0 151.9 / 158.6 / 3 (1,047.3 / 1,093.5 / 3) 2.6 / 2.9

 K254

 33.7 141.2 / 144.7 / 2 (973.5 / 997.7 / 2) 3.3 / 3.3 33.0 151.7 / 158.1 / 1 (1,045.9 / 1,090.1 / 1) 2.3 / 3.7

 K259

 31.8 151.0 / 157.3 / 2 (1,041.1 / 1,084.5 / 2) 4.0 / 5.2 33.3 150.8 / 156.9 / 2 (1,039.7 / 1,081.8 / 2) 2.3 / 2.9

 K260

 32.4 149.9 / 156.3 / 3 (1,033.5 / 1,077.6 / 3) 3.8 / 3.8 35.3 148.6 / 154.1 / 3 (1,024.6 / 1,062.5 / 3) 2.9 / 4.3

 K261

 31.9 150.9 / 157.1 / 2 (1,040.4 / 1,083.2 / 2) 3.8 / 5.2 34.4 151.0 / 157.6 / 2 (1,041.1 / 1,086.6 / 2) 2.6 / 4.3

twenty

Example 11 - Effect of treatment.

Sections of the cast iron bar in RN032037 plant were treated, the composition of which is indicated in Table 20, from a hot rolled plate and milled in coil in a 0.600 ”(15.24 mm) thick plant. The samples were further treated by the various treatment routes shown in Fig. 30. Method A involved a cold rolling at 0.012 "(0.3 mm) and a heat treatment in solution in a fluidized bed furnace for 60 seconds at 950 ° C, a stabilization annealing at 500 ° C for 3 hours, a 25% cold lamination at 0.009 "(0.23 mm), and a second annealing was given at 350 ° C for 4 hours. the BF procedure, the metal was rolled at 0.050 "(1.3 mm) and an intermediate bell anneal (" IMBA ") of 575 ° C was given for 8 hours, then the samples were subjected to cold rolling at 0.012 "(0.3 mm) and at a heat treatment in solution in a fluidized bed furnace for 60 seconds at 950 ° C, an annealing stabilization at 500 ° C for 3 hours, a 25% cold lamination at 0.009 "(0.23mm), and they were given a second

5

10

fifteen

twenty

25

30

35

40

Four. Five

Annealing at 350 ° C for 4 hours. In procedure C, the alloy was rolled at 0.024 "(0.61 mm) and subjected to a heat treatment in solution in a fluidized bed furnace for 60 seconds at 950 ° C, followed by cold rolling at 0.012" (0.3 mm) and a second heat treatment in solution in a fluidized bed furnace for 60 seconds at 950 ° C. Subsequently, the procedure involved an annealing of stabilization at 500 ° C for 3 hours, a cold rolling at 25 % at 0.009 "(0.23 mm), and a second anneal was given at 350 ° C for 4 hours. In procedure D, a cold rolling at 0.012" (0.3 mm) followed by a heat treatment in solution In a fluidized bed furnace for 60 seconds at 950 ° C, the alloy was 25% cold rolled at 0.009 "(0.23 mm), stabilized annealed at 475 ° C for 3 hours, laminated 22% cold at 0.007 ”(0.18 mm), and a final anneal of 300 ° C was given for 3 hours. In procedure E, the metal was rolled at 0.050 "(1.27 mm) and an intermediate bell anneal of 575 ° C was given for 8 hours. Then, the samples were laminated at 0.024 "(0.61 mm) and heat treated in solution in a fluidized bed furnace for 60 seconds at 950 ° C, followed by cold rolling at 0.012" (0.3 mm) and a second heat treatment in solution in a fluidized bed oven for 60 seconds at 950 ° C. Subsequently, the procedure involved an annealing of stabilization at 500 ° C for 3 hours, a 25% cold lamination at 0.009 ”(0 , 23 mm), and a second annealing was given at 350 ° C for 4 hours.

 Table 24: Properties resulting from the procedures of Example 11

 Process

 Description YS / TS / EI ksi / ksi /% (MPa / MPa /%)% IACS 90 ° MBR / t

 TO

 "Standard" procedure 145.1 / 152.7 / 3 (1,000.4 / 1,052.8 / 3) 36.2 4.0 / 7.0

 B

 IMBA procedure 144.4 / 150.4 / 3 (995.6 / 1.037.0 / 3) 37.4 3.8 / 4.0

 C

 Double annealing procedure in solution 147.2 / 152.7 / 3 (1,014.9 / 1,052.8 / 3) 37.1 3.6 / 6.9

 0

 Procedure SA-CR-stabilization-CR-stabilization 146.5 / 154.4 / 2 (1,010.1 / 1,064.5 / 2) 34.2 4.2 / 8.7

 AND

 IMBA-Doble SA procedure 143.6 / 150.1 / 3 (990.1 / 1.034.9/3) 36.7 3.3 / 7.0

Example 12 - Effect of treatment.

Sections of the RN032037 plant cast bar were treated, the composition of which is indicated in Table 20, from a hot-rolled plate milled in a 0,600 ”(15.24 mm) thick plant coil. The procedure variables were systematically varied to explore a matrix that contained intervals of treatment conditions. Figure 31 is a flow chart of the procedure of this Example 12. After cold rolling at 0.012 "(0.3 mm), the samples were annealed in solution in a fluidized bed furnace at temperatures of 925, 950 , 975 and 1,000 ° C for 60 seconds. Then, the samples were given annealing stabilization at temperatures of 450, 475, 500 and 525 ° C for three hours. Then, the samples were cold rolled to the final thickness with different reductions of 15, 25 and 35%. Finally, the samples were given a second annealing of stabilization for four hours at 300, 325, 350 and 375 ° C. Table 25 contains the properties of the samples with different annealing temperatures in solution, while the rest of the procedure remained constant. As the temperature of the solution increased, the elasticity limit increased, while the conductivity decreased. Additionally, the folding formability worsened at higher annealing temperatures in solution, due to the large grain size that arose during annealing at 975 and 1,000 ° C. Therefore, an annealing in solution with a grain size of less than 20 pm was preferred.

When the temperature of the first stabilization was varied, while the other treatment variables were kept constant, it was found that the highest levels of mechanical resistance were due to intermediate stabilization temperatures, as shown in Table 26 for stabilization at 475 and 500 ° C. In addition, the conductivity increased with the increase in the stabilization temperature. Therefore, the temperature of the first stabilization can be manipulated to provide various desired combinations of mechanical strength and conductivity.

When the rolling reduction between the first and second stabilizations was varied, it was found that the elasticity limit increased with the increase of the reduction, in this case up to 35%, while the conductivity was not affected. A greater increase in mechanical resistance was found when a reduction of 15 to 25% was passed than when it was increased from 25 to 35%. It was found that folding formability worsened with greater reductions. The lamination reduction can be manipulated to affect the characteristics of the mechanical-formability resistance of the material produced. The use of a rolling reduction above 35% may be useful to produce maximum strength, although with a lower conformability.

Table 28 shows that the second stabilization annealing temperature does not have a great effect on the

properties, when the other treatment variables remain constant. The conductivity was found to increase as the temperature of the second stabilization increased, but to a lesser degree. Therefore, a wide range of operation was acceptable for this stage of the procedure.

 Table 25: Effect of the variation of the annealing temperatures in solution, with a first stabilization at 475 ° C, a lamination with a reduction of 25%, a second stabilization at 350 ° C of Example 12

 SA temperature, ° C

 Grain size of SA, | jm YS / TS / EI ksi / ksi /% (MPa / MPa /%)% lACS Folded at 90 °

 925

 9.0 142.3 / 147.7 / 3 (981.1 / 1.018.4 / 3) 36.0 6.0 / 6.0

 950

 12.9 145.9 / 152.3 / 3 (1,005.9 / 1,050.1 / 3) 34.1 6.1 / 6.1

 975

 26.1 146.5 / 152.6 / 2 (1,010.1 / 1,052.1 / 2) 32.3 6.1 / 12.1

 1,000

 28.8 147.5 / 152.1 / 3 (1,017.0 / 1,048.7 / 3) 32.7 8.7 / 12.1

 Table 26: Effect of the variation of the temperatures of the first stabilization, with an annealing in solution at 475 ° C, a lamination with a reduction of 25%, a second stabilization at 350 ° C of Example 12

 Temperature of the first stabilization, ° C

 YS / TS / EI ksi / ksi /% (MPa / MPa /%)% lACS Folded at 90 °

 450

 140.1 / 145.2 / 4 (966.0 / 1.001.1 / 4) 30.5 4.0 / 6.1

 475

 145.9 / 152.3 / 3 (1,005.9 / 1,050.1 / 3) 34.1 6.1 / 6.1

 500

 145.1 / 152.7 / 3 (1,000.4 / 1,052.8 / 3) 36.2 4.0 / 7.0

 525

 133.2 / 134.5 / 1 (918.4 / 927.3 / 1) 39.9 n / m *

5 * not measured

 Table 27: Effect of variation of lamination reductions, with an annealing in solution at 950 ° C, a first stabilization at 475 ° C, a second stabilization at 350 ° C

 Lamination Reduction

 YS / TS / EI ksi / ksi /% (MPa / MPa /%)% lACS Folded at 90 °

 fifteen%

 138.4 / 145.0 / 4 (954.2 / 999.7 / 4) 33.9 5.4 / 5.4

 25%

 145.9 / 152.3 / 3 (1,005.9 / 1,050.1 / 3) 34.1 6.1 / 6.1

 35%

 148.9 / 155.5 / 3 (1,026.6 / 1,072.1 / 3) 34.0 7.1 / 10.0

 Table 28: Effect of the variation of the temperatures of the second stabilization, with an annealing in solution at 950 ° C, a first stabilization at 475 ° C, a lamination with a reduction of 25%

 Second stabilization temperature, ° C

 YS / TS / EI ksi / ksi /% (MPa / MPa /%)% lACS Folded at 90 °

 300

 146.4 / 152.0 / 2 (1,009.4 / 1,048.0 / 2) 33.2 6.1 / 6.1

 325

 146.5 / 152.3 / 3 (1,010.1 / 1,050.1 / 3) 33.6 6.1 / 8.7

 350

 145.9 / 152.3 / 3 (1,005.9 / 1,050.1 / 3) 34.1 6.1 / 6.1

 375

 146.2 / 152.7 / 3 (1,008.0 / 1,052.8 / 3) 34.8 6.0 / 8.6

Samples were laminated in the laboratory from the plant casting bar without Cr RN033407 (composition in

5

10

fifteen

twenty

25

30

35

40

Table 20) from the condition of coil milling at 0.460 "(11.7 mm) to 0.012" (0.3 mm). Subsequently, the samples were heat treated in solution in a fluidized bed oven for 60 seconds at 900 The samples were then laminated at 25% to 0.009 "(0.23 mm) and annealed and stabilized at 425, 450 and 475 ° C for times of 4 and 8 hours, for each temperature. Samples were cold rolled at 22% at 0.007 "(0.18 mm) and given a final anneal of 300 ° C for three hours. The best combination of mechanical resistance and conductivity occurred at 450 ° C for 8 hours of stabilization, the properties of that condition and others being indicated in Table 28a. When comparing the 450 ° C / 8 hour data with the properties of Table 25, it is clear that reducing the annealing temperature in solution to 900 ° C further reduces the yield limit and increases the conductivity to produce the unique combination 140 ksi (965 MPa) and 39% IACS. In addition, the treatment that included an annealing temperature in solution of 900 ° C produced an improved folding formability compared to the treatment that involved higher annealing temperatures in solution.

 Table 28A: Properties after a treatment that includes an annealing in solution at 900 ° C

 Condition of the first stabilization

 Grain size of SA, | jm YS / TS / EI ksi / ksi /% (MPa / MPa /%)% lACS Folded at 90 °

 450 ° C / 4 h

 5.5 138.5 / 143.0 / 2 (954.9 / 985.9 / 2) 36.1 2.6 / 4.0

 450 ° C / 8 h

 5.5 140.3 / 144.7 / 2 (967.3 / 997.7 / 2) 39.0 2.0 / 4.3

 475 ° C / 4 h

 5.5 126.9 / 131.7 / 3 (874.9 / 908.0 / 3) 40.7 2.3 / 4.0

 475 ° C / 8 h

 5.5 131.0 / 135.0 / 3 (903.2 / 930.8 / 3) 41.2 1.7 / 2.3

Example 13 - Effect of Si and Mg.

Laboratory ingots were melted in a graphite crucible with the compositions indicated in Table 29 and Tamman was applied to steel molds which, after opening, were 4.33 ”x 2.17” x 1 , 02 "(110 mm x 55 mm x 26 mm). All alloys were chosen to have a Cr content of 0.5%. The Si content was varied between 1.0% and 1.5%. the variants with a high Si content of 1.5%, the Ni / Co ratio varied between 4.98 and 11.37 with a stoichiometric ratio ((Ni + Co) / (Si-Cr / 5)) set at around of 4. The influence of Mg for the BW alloy was tested, with the same alloy composition as BV but additionally with 0.1% Mg.

Figure 32 is a flow chart of the procedure of this Example 13. After homogenizing them for two hours at 900 ° C, they were hot rolled at 0.472 "(12 mm), thereby reheating after each pass at 900 ° C for 10 minutes. After the last pass, the bars were tempered in water. After roughing and milling at 0.394 ”(10 mm) in order to remove surface oxide, the alloys were cold rolled to 0.012" (0.3 mm) and heat treated in solution in a fluidized bed furnace with the time and temperature indicated in Table 29. Time and temperature were selected to achieve grain sizes below 20 pm.

Subsequently, the alloys were cold rolled 25% at 0.009 "(0.23 mm) and then subjected to a stabilization annealing of 450 and 475 ° C for 3 hours. Table 30 shows the properties of the samples. The formability was measured by means of a V-groove block. With the increase in Si content, the elasticity limit increased from 121 ksi (834 MPa), for the alloy with 1.05% Si, to 135 ksi ( 931 MPa), for the alloy with 1.51% Si. For variants with 1.16% Si, Mg resulted in an improvement of the elasticity limit of 5-7 ksi (34-48 MPa). The reduction of the Ni / Co ratio from 11.37 to 4.98 improved the elasticity limit for alloys with a high Si content (1.5%). Stress relaxation was tested by the ring method with an initial target tension of 0.8 times the elasticity limit. Table 31 shows the stress relaxation data for the BV, BW and BX variants. When comparing the BV and the BW, due to the addition of Mg, it was observed that the resistance to stress relaxation increased from 66.3% to 86.6%, for the condition of 150 ° C / 1,000 h, and the 48.5% to 72.3%, for the condition of 200 ° C / 1,000 h. The stress relaxation resistance of the BX that contained more If it amounted to 82.3%, for the condition of 150 ° C / 1,000 h, and 68.7%, for the condition of 200 ° C / 1,000 h.

Table 29: Alloys of Examples 13 and 15,% by weight.

 Alloy

 Ni Co Cr Si Mg Ratio * Ni / Co SA conditions Grain size, jm

 BU

 3.08 0.69 0.57 1.05 4.03 4.46 950 ° C -1 minute 10-15

 BV

 3.51 0.75 0.49 1.16 4.01 4.68 950 ° C -1 minute 10-15

 Bw

 3.52 0.78 0.51 1.16 0.11 4.06 4.51 950 ° C -1 minute 15

 BT

 4.04 1.15 0.47 1 41 3.94 3.51 950 ° C -1 minute 5

 Bx

 4.89 0.43 0.50 1.48 3.86 11.37 950 ° C -1 minute 15-20

 BY

 4.48 0.90 0.51 1.51 3.82 4.98 950 ° C -1 minute 10

* Ratio = (Ni + Co) / (Si-Cr / 5)

Table 30: Properties of the SA-Cr-AA procedure of Example 13.

 Alloy

 AA T, ° C YS, ksi (MPa)% lACS 90 ° MINBR / t

 BU

 450 121.0 (834.3) 27.6 2.2 / 1.3

 BV

 450 121.8 (839.8) 32.5 1.7 / 1.3

 475

 120.5 (830.8) 34.8 n.m.

 Bw

 450 126.9 (874.9) 31 8 2.2 / 2.6

 475

 127.6 (879.8) 34.4 n.m.

 BT

 450 127.5 (879.1) 28.6 n.m.

 475

 128.9 (888.7) 32.1 n.m.

 Bx

 450 129.5 (892.9) 29 1 2.6 / 2.6

 475

 125.9 (868.1) 31.1 n.m.

 BY

 450 135.2 (932.2) 30 2.2 / 2.2

 475

 134.0 (923.9) 31.4 3.4 / 2.1

Table 31: Stress relaxation of the 25% SA-CR procedure - AA 450 ° C / 3 h of Example 13.

 Alloy

 YS, ksi (MPa)% lACS Remaining voltage (%)

 150 ° C / 1,000 h

 200 ° C / 1,000 h

 BV

 121.8 (839.8) 32.5 66.3 48.5

 Bw

 126.9 (874.9) 31.8 86.6 72.3

 Bx

 129.5 (892.9) 29.1 82.3 68.7

5

Example 14 - Effect of Si and Mg.

Figure 33 is a flow chart of the procedure of this Example 14. Test specimens of Example 13 were subsequently cold rolled to 0.007 "(0.18 mm) with a cold reduction of 22%. After that, the samples were annealed and stabilized at temperatures of 300 to 400 ° C for 3 hours. Table 32 shows the properties of the samples that were given a second stabilization at 300 ° C. The formability was measured by means of a V-groove block.

The highest elasticity limit was achieved with the first stabilization temperature of 450 ° C. As the Si content increased, the elasticity limit increased from 131 ksi (903 MPa), for the 1.05% Si alloy, to 147 ksi (1,014 MPa), for the 1.51% Si alloy. For the 1.16% Si variants, Mg resulted in an improvement of the elastic limit of 7-10 ksi (48-69 MPa). The reduction of the Ni / Co ratio from 11.37 to 4.98 improved the elasticity limit by 3 ksi (21 MPa) for alloys with a high Si content of 1.5%. Stress relaxation was tested by the ring method, with an initial target tension of 0.8 times the elasticity limit. The

Table 33 shows the stress relaxation data for BV, BW and BX with the SA-CR-1.AA 450 ° C-CR-2.AA 300 ° C procedure.

When comparing the alloys BV and BW, due to the addition of Mg, it was observed that the resistance to stress relaxation increased from 72.6% to 85.6%, for the condition of 150 ° C / 1,000 h, and of 55.8% to 69.3%, for condition 5 of 200 ° C / 1,000 h. The stress relaxation resistance of the BX alloy with a higher Si content amounted to 81.1%, for the condition of 150 ° C / 1,000 h, and 66.1%, for the condition of 200 ° C / 1,000 h

Table 32: Properties of the SA-CR-1.AA-CR-2.AA procedure of Example 14.

 Alloy

 Temp. 1.AA, ° C 2.AA 300 ° C / 3 h

 YS ksi (MPa)

 TS ksi (MPa) A10,%% lACS 90 ° MINBR / t

 BU

 450 130.7 (901.1) 138 1 (958.4) 2.6 33.6 5.5 / 5.5

 BV

 450 137.4 (947.3) 144.5 (996.3) 3.7 31.4 2.8 / 5.6

 475

 130.8 (901.8) 137.8 (950.1) 4.8 34.8 2.8 / 5.0

 Bw

 450 144.0 (992.8) 143.6 (990.1) 23 32.1 3.3 / 7.8

 475

 141.3 (974.2) 147.1 (1,014.2) 3.8 34 2.8 / 6.7

 BT

 450 144.6 (997.0) 152.4 (1,050.8) 2.9 29.8 4.0 / 8.0

 475

 137.8 (950.1) 146.2 (1,008.0) 4.2 34.1 4.0 / 7.0

 Bx

 450 143.7 (990.8) 155.2 (1,070.1) 2.8 28.6 3.3 / 7.8

 475

 134.4 (926.7) 148.2 (1,021.8) 2.8 31.2 2 8 / 6.7

 BY

 450 146.6 (1,010.8) 146.6 (1,010.8) 155.8 3 3.3 / 6.7

 475

 137.6 (948.7) 150.0 (1,034.2) 4.3 32.2 3.3 / 6.7

Table 33: Relaxation of stresses of the SA-CR-1.AA 450 ° C-CR-2.AA 300 ° C procedure of Example 14.

 Alloy

 YS ksi (MPa)% lACS Remaining voltage (%)

 150 ° C / 1,000 h

 200 ° C / 1,000 h

 BV

 137.4 (947.3) 31.4 72.6 55.8

 Bw

 144.0 (992.8) 32.1 85.6 69.3

 Bx

 143.7 (990.8) 28.6 81.1 66.1

10

Example 15 - Effect of Si and Mg.

Laboratory ingots were melted in a graphite crucible with the compositions indicated in Table 34 and Tamman was applied to steel molds which, after opening, were 4.33 "x 2.17" x 1 , 02 "(110 mm x 55 mm x 26 mm). The alloys had no Cr and the stoichiometric ratio ((Ni + Co) / (Si-Cr / 5)) was about 15 around 4.2. The Ni ratio / Co was about 4.5. Two of the alloys had a target Si content of 1.1%, but differed in the Mg content, and another alloy had a Si content of 1.4% and additionally Mg. Figure 34 is a flow chart of the procedure of this Example 15. After a two-hour homogenization at 900 ° C, they were hot rolled at 0.472 "(12 mm), thereby reheating after each pass at 900 ° C for 10 minutes After the last pass, the bars were quenched in 20 water, after roughing and milling at 0.394 ”(10 mm) in order to remove the rust On the surface, the alloys were cold rolled at 0.012 "(0.3 mm) and heat treated in solution in a fluidized bed furnace for the time and temperature indicated in Table 34. Time and temperature were selected to achieve Grain sizes below 20 pm.

Subsequently, the alloys were cold rolled 25% at 0.009 "(0.23 mm) and then subjected to a stabilization annealing of 450 and 475 ° C for 3 hours. Table 35 shows the properties of the samples. The elasticity limit, the formability measured with a V-groove block and the conductivity of FL and FM, which do not contain Cr, are similar to those of BV and BW, which contain Cr, of Example 13, with a content Si 5 of 1.1%, a comparable Ni / Co ratio and a stoichiometric ratio. As in Example 13, the addition of 0.1% Mg resulted in an improvement of the elastic limit of 7-8 ksi (48-55 MPa).

With the increase in the Si content from 1.17% to 1.39%, the elasticity limit increased from 126.6 ksi (873 MPa) to 130.5 ksi (900 MPa), at the same annealing temperature in solution . For the FN variant, the increase in annealing temperature in solution from 950 ° C to 1,000 ° C resulted in an increase in the elasticity limit of 10 ksi 10 (69 MPa).

Stress relaxation was tested by the ring method, with an initial target tension of 0.8 times the elasticity limit. Table 36 shows the stress relaxation data for procedures with an annealing temperature in solution of 950 ° C. The relaxation of FL and FM stresses was slightly lower, compared to BV and BW samples with 1.16% Si, containing Cr, from Example 13. Similar to Example 13, the addition of 0, 1% Mg resulted in an increase in stress relaxation from 64.6% to 82.7%, for the condition of 150 ° C / 1,000 h, and from 44.3% to 69.2%, for 200 ° C / 1,000 h condition. The stress relaxation resistance of the FN variant with 1.39% Si, containing Mg, amounted to 84.1%, for the 150 ° C / 1,000 h condition, and 65.9%, for the condition 200 ° C / 1,000 h.

 Table 34: Alloys of Examples 15 and 16,% by weight

 Alloy

 Ni Co Cr Si Mg Ratio * Ni / Co SA Conditions Grain size, pm

 FL

 3.71 0.90 1.09 4.23 4.12 950 ° C -1 minute 10

 FM

 3.89 0.87 1.17 0.10 4.05 4.47 950 ° C -1 minute 5-10

 FN

 5.19 0.99 1.39 0.10 4.47 4.90 950 ° C -1 minute 10

 1,000 ° C -1 minute

 15-20

* Ratio = (Ni + Co) / (Si-Cr / 5)

20 Table 35: Properties of the SA-CR-AA procedure of Example 15.

 Alloy

 SA conditions AA T, ° C YS ksi (MPa)% lACS 90 ° MINBR / t GW / BW

 FL

 950 ° C -1 minute 450 118.6 (817.7) 29.5 2.6 / 1.3

 475

 119.4 (823.2) 34.5 3.0 / 1.7

 FM

 950 ° C -1 minute 450 126.6 (872.9) 30.2 2.6 / 2.2

 475

 126 (868.7) 33.1 2.1 / 2.1

 FN

 950 ° C -1 minute 450 130.5 (899.8) 30.7 3.0 / 2.6

 475

 129.1 (890.1) 33.1 2.6 / 2.2

 1,000 ° C -1 minute

 450 141.7 (977.0) 27.1 3.5 / 3.9

 475

 139.2 (959.8) 29.6 3.5 / 4.8

Table 36: Relaxation of stresses of the SA 950 ° C-CR 25% -AA 450 ° C / 3 h procedure of Example 15.

 Alloy

 YS ksi (MPa)% lACS Remaining voltage (%)

 150 ° C / 1,000 h

 200 ° C / 1,000 h

 FL

 118.6 (817.7) 29.5 64.6 44.3

5

10

fifteen

twenty

25

 FM

 126.6 (872.9) 30.2 82.7 69.2

 FN

 130.5 (899.8) 30.7 84.1 65.9

Example 16 - Effect of Si and Mg.

Figure 35 is a flow chart of the procedure of this Example 16. Test tubes of Example 15 were subsequently cold rolled to 0.007 "(0.18 mm) with a cold reduction of 22%. After that, the samples were annealed and stabilized at temperatures of 300 to 350 ° C for 3 hours. Table 37 shows the properties of the samples that were given a second stabilization at 300 ° C. The formability was measured by a V-groove block. The highest elasticity limit was achieved with the first stabilization temperature of 450 ° C.

FM showed a higher elasticity limit at 11 ksi (76 MPa), compared to FL1, which is partially attributed to the Mg content and partially attributed to the slightly higher Si content. The limit of elasticity, folding and conductivity of FL and FM, which did not contain Cr, were similar to those of BV and BW, which contained Cr, of example 15, with a Si content, a Ni / Co ratio and a stoichiometric relationship comparable.

The increase in Si content from 1.17% to 1.39% led to the same elasticity limit of approximately 144 ksi (993 MPa) for a solution annealing temperature of 950 ° C. For the FN variant, the increase in annealing temperature in solution from 950 ° C to 1,000 ° C resulted in an increase in the elasticity limit from 143 ksi (986 MPa) to 158 ksi (1,089 MPa).

Stress relaxation was tested by the ring method, with an initial target tension of 0.8 times the elasticity limit. Table 38 shows the relaxation data of the FL and FM voltages for the SA 950 ° C-CR-1.AA 450 ° C-CR-2.AA 300 ° C procedure. The relaxation of FL and FM stresses was 2-3% lower, compared to BV and BW samples with 1.16% Si, containing Cr, from Example 15. Similar to example 15, an addition 0.1% Mg resulted in an increase in stress relaxation from 70.0% to 82.0%, for the condition of 150 ° C / 1,000 h, and from 52.3% to 66.9% , for the condition of 200 ° C / 1,000 h. The stress relaxation resistance of the fN variant with 39% Si, containing Mg, amounted to 85.0%, for the condition of 150 ° C / 1,000 h, and 66.4%, for the condition of 200 ° C / 1,000 h.

Table 37: Properties of the SA-CR-1.AA-CR-2.AA procedure of Example 16.

 Alloy

 Conditions of SA Temp. 1.AA, ° C 2.AA 300 ° C / 3 h

 YS ksi (MPa)

 TS ksi (MPa) A10,%% lACS 90 ° MINBR / t GW / BW

 FL

 950 ° C -1 minute 450 133.1 (917.7) 140 (965.3) 2.7 31.6 4.5 / 6.1

 475

 129.7 (894.2) 139.5 (961.8) 1.9 36.2 3.9 / 4.4

 FM

 950 ° C -1 minute 450 144 (992.8) 147.6 (1,017.7) 2 31 4.4 / 7.2

 475

 141.3 (974.2) 145 (999.7) 1.8 33.2 4.5 / 6.8

 FN

 950 ° C -1 minute 450 143.2 (987.3) 150.0 (1,034.2) 2 31.5 3.9 / 7.2

 475

 133.1 (917.7) 138.9 (957.7) 2.4 34.3 3.3 / 5.6

 1,000 ° C -1 minute

 450 158.1 (1,090.1) 165.1 (1,138.3) 1.4 27.6 5.0 / 9.4

 475

 157.5 (1,085.9) 164.6 (1,134.9) 1.9 30.9 4.4 / 8.3

Table 38: Stress relaxation of the SA 950 ° C-CR-1.AA 450 ° C-CR-2.AA 300 ° C procedure of Example 16.

 Alloy

 YS ksi (MPa)% lACS Remaining voltage (%)

 150 ° C / 1,000 h

 200 ° C / 1,000 h

 FL

 133.1 (917.7) 31.6 70.1 52.3

 FM

 144.0 (992.8) 31 82.0 66.9

 FN

 143.2 (987.3) 31.6 85.0 66.4

Figure 36 shows the relationship between 90 ° -minBR / t of the BW and the elastic limit for the alloys and procedures of Examples 13, 14, 15 and 16. The two procedures, SA-CR-AA and SA- CR-AA-CR-AA, form two groups with a certain conformability-limit elasticity relationship. The solid lines are only a guideline 5 for the observation and mark the increase of the Min BR / t and the increase of the elasticity limit, with the higher Si content and / or with the addition of Mg. There was almost no difference in the limit of elasticity and the relationship of formability-limit of elasticity between variants that did not contain Cr and those that contained Cr.

Figure 37 shows the relationship between% IACS and the elasticity limit for the alloys and procedures of Examples 13, 14, 15 and 16. Alloys that did not contain Cr and those that contained Cr showed the same ability to achieve 30% IACS conductivity, together with a high limit of elasticity. The SA-CR-AA-CR-AA procedure achieved a higher elasticity limit than the SA-CR-AA procedure, but with the same conductivity.

Claims (4)

5 10 fifteen twenty 25 1. - A copper-based alloy that has an improved combination of elasticity limit, electrical conductivity and resistance to stress relaxation, consisting of: between 3.5 and 3.9 percent by weight of Ni; between 0.8 and 1.0 percent by weight of Co; between 1.0 and 1.2 percent by weight of Si; between 0.05 and 0.15 percent by weight of Mg; up to 0.1 weight percent Cr; up to 1.0 percent by weight of Sn, and up to 1.0 percent by weight of Mn, the remainder being copper and impurities, where the Ni / Co ratio is between 3 and 5, the alloy being treated to have an elasticity limit of at least 140 ksi (965 MPa) and an electrical conductivity of at least 30% IACS . 2. - The alloy according to claim 1, wherein the ratio (Ni + Co) / (Si-Cr / 5) is between 3.5 and 5.0. 3. - A process for manufacturing a copper-based alloy according to one of the preceding claims, comprising: melt and strain the alloy; hot rolling from 750 to 1,050 ° C; cold rolling to a convenient caliber to solubilize; anneal the alloy between 800 and 1,050 ° C for 10 seconds to one hour; Y subsequently, temper in water, or cool rapidly, the alloy at room temperature to obtain an electrical conductivity of less than 20% IACs (11.6 MS / m) and an equiaxial grain size of 5-20 pm; cold rolling the alloy to obtain a thickness reduction of 0 to 75%; subject the alloy to a hardening annealing of 300 to 600 ° C for 10 minutes to 10 hours; subsequently, cold roll the alloy to obtain a thickness reduction of 10 to 75% to finish the calibration; subject the alloy to a second annealing of hardening and stabilization of 250 to 500 ° C for 10 minutes to 10 hours. 4. - The method according to claim 3, which after hot rolling further comprises an intermediate recrystallization annealing.