Nickel-cobalt based alloys

Abstract: This invention relates to nickel-cobalt based alloys comprising the following elements in percent by weight: from about 0.002 to about 0.07 percent carbon, from about 0 to about 0.04 percent boron, from about 0 to about 2.5 percent columbium, from about 12 to about 19 percent chromium, from about 0 to about 6 percent molybdenum, from about 20 to about 35 percent cobalt, from about 0 to about 5 percent aluminum, from about 0 to about 5 percent titanium, from about 0 to about 6 percent tantalum, from about 0 to about 6 percent tungsten, from about 0 to about 2.5 percent vanadium, from about 0 to about 0.06 percent zirconium, and the balance nickel plus incidental impurities, the alloys having a phasial stability number N v3B less than about 2.60. Furthermore, the alloys have at least one element selected from the group consisting of aluminum, titanium, columbium, tantalum and vanadium. Also, the alloys have at least one element selected from the group consisting of tantalum and tungsten. Articles for use at elevated temperatures, such as fasteners, can be suitably made from the alloys of this invention.

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to nickel-cobalt based alloys and, more particularly, high strength nickel-cobalt based alloys and articles made therefrom having increased thermal stability and microstructural stability at elevated temperatures. 2. Description of the Prior Art There has been a continuing demand in the metallurgical industry for alloy compositions which have high strength combined with increased thermal stability and microstructural stability for use in applications subject to higher service temperatures. For example, advances over recent years in the design of gas turbines have resulted in engines which are capable of operating at higher temperatures, pressure ratios and rotational speeds, which assist in providing increased engine efficiencies and improved performance. Accordingly, alloys used to produce components in these engines, such as fastener components, must be capable of providing the higher temperature properties necessary for use in these advanced engines operating at the higher service temperatures. Suggestions of the prior art for nickel-cobalt based alloys include U.S. Patent No. 3,356,542, Smith, which discloses certain nickel-cobalt based alloys containing in weight percentage 13-25% chromium and 7-16% molybdenum. These alloys, which are commercially known as MP35N alloys, are claimed to be corrosion resistant and capable of being work-strengthened under certain temperature conditions, whereby very high ultimate tensile and yield strengths are developed (MP35N is a registered trademark of SPS Technologies, Inc., assignee of the present application). Furthermore, these alloys have phasial constituents which can exist in one or two crystalline structures, depending on temperature. They are also characterized by composition-dependent transition zones of temperatures in which transformations between phases occur. For example, at temperatures above the upper temperature limit of the transformation zone, the alloys are stable in the face-centered cubic ("FCC") structure. At temperatures below the lower temperature of the transformation zone, the alloys are stable in the hexagonal close-packed ("HCP") form. This transformation is sluggish and cannot be thermally induced. However, by cold working metastable face-centered cubic material at a temperature below the upper limit of the transformation zone, some of it is transformed into the hexagonal close-packed phase which is dispersed as platelets throughout a matrix of the face-centered cubic material. It is this cold working and phase transformation which is indicated to be responsible for the ultimate tensile and yield strengths of these alloys. However, the MP35N alloys described in the Smith patent have stress-rupture properties which make them unsuitable for use at temperatures above about 427°C (800°F). U.S. Patent No. 3,767,385, Slaney, discloses certain nickel-cobalt alloys, which are commercially known as MP159 alloys (MP159 is a registered trademark of SPS Technologies, Inc.). The MP159 alloys described in the Slaney '385 patent are an improvement on the Smith patent alloys. As described in the Slaney '385 patent, the composition of the alloys was modified by the addition of certain amounts of aluminum, titanium and niobium in order to take advantage of additional precipitation hardening of the alloy, thereby supplementing the hardening effect due to conversion of FCC to HCP phase. The alloys disclosed include elements, such as iron, in amounts which were formerly thought to result in the formation of disadvantageous topologically close-packed (TCP) phases such as the sigma, mu or chi phases (depending on composition), and thus thought to severely embrittle the alloys. But this disadvantageous result was said to be avoided with the invention of the Slaney patent. For example, the alloys of the Slaney patent are reported to contain iron in amounts from 6% to 25% by weight while being substantially free of embrittling phases. According to the Slaney '385 patent, it is not enough to constitute the described alloys within the specified ranges in weight percentage of 18-40% nickel, 6-25% iron, 6-12% molybdenum, 15-25% chromium, 0 or 1-5% titanium, 0 or 0-1% aluminum, 0 or 0-2% niobium, 0-0.05% carbon, 0-0.1% boron, and balance cobalt. Rather, the alloys must further have an electron vacancy number (N v ), which does not exceed certain fixed values in order to avoid the formation of embrittling phases. The N v number is the average number of electron vacancies per 100 atoms of the alloy. By using such alloys, the Slaney '385 patent states that cobalt based alloys which are highly corrosion resistant and have excellent ultimate tensile and yield strengths can be obtained. These properties are disclosed to be imparted by formation of a platelet HCP phase in a matrix FCC phase and by precipitating a compound of the formula Ni 3 X, where X is titanium, aluminum and/or niobium. This is accomplished by working the alloys at a temperature below the upper temperature of a transition zone of temperatures in which transformation between HCP phase and FCC phase occurs and then heat treating between 427°C (800°F) and 732°C (1350°F) for about 4 hours. Nevertheless, the MP159 alloys described in the Slaney '385 patent have stress-rupture properties which make them unsuitable for use at temperatures above about 593°C (1100°F). Another suggestion of the prior art is U.S. Patent No. 4,795,504, Slaney, which discloses alloys (known as MP210 alloys) having a composition in weight percentage of 0.05% max carbon, 20-40% cobalt, 6-11% molybdenum, 15-23% chromium, 1.0% max iron, 0.005-0.020% boron, 0-6% titanium, 0-10% niobium and the balance nickel. The alloys disclosed in this patent are said to retain satisfactory tensile and ductility levels and stress-rupture properties at temperatures of about 704°C (1300°F). In order to avoid formation of embrittling phases, such as the sigma phase, it is also disclosed that the electron vacancy number N V for these alloys cannot be greater than 2.80. Again, these alloys are disclosed as being strengthened by working at a temperature which is below the HCP-FCC transformation zone. Further, the alloys described in this patent, like those described in the above-mentioned Smith patent and Slaney '385 patent, are multiphase alloys forming an HCP-FCC platelet structure. Additionally, U.S. Patent No. 4,908,069, discloses an invention premised upon the recognition that advantageous mechanical properties (such as high strength), and high hardness levels, can be attained in certain alloy materials having high resistance to corrosion through formation of a gamma prime phase in those materials and the retention of a substantial gamma prime phase after the materials have been worked to cause formation of an HCP platelet phase in an FCC matrix. In one aspect, this patent describes a certain method of making a work-strengthenable alloy which includes a gamma prime phase. This method comprises: forming a melt containing, in percent by weight, 6-16% molybdenum, 13-25% chromium, 0-23% iron, 10-55% nickel, 0-0.05% carbon, 0-0.05% boron, and the balance (constituting at least 20%) cobalt, wherein the alloy also contains one or more elements which form gamma prime phase with nickel and has a certain defined electron vacancy number (N V ); cooling the melt; and heating the alloy at a temperature from 600°-900°C for a time sufficient to form the gamma prime phase, prior to strengthening of the alloy by working it to achieve a reduction in cross-section of at least 5%. Furthermore, U.S. Patent No. 4,931,255, discloses nickel-cobalt alloys having, in weight percentage, 0-0.05% carbon, 6-11% molybdenum, 0-1% iron, 0-6% titanium, 15-23% chromium, 0.005-0.020% boron, 1.1-10% niobium, 0.4-4.0% aluminum, 30-60% cobalt and the balance nickel, wherein the alloys have a certain defined electron vacancy number (N V ). Several of the alloys described in the above-mentioned patents, such as the MP35N alloy and MP159 alloy, have been utilized in aerospace fastener components. Additionally, the alloy commonly known as Waspaloy is widely used to make aerospace fastener components. Waspaloy has a composition reported in AMS 5707G and AMS-5708F Specifications of, in weight percentage, 0.02-0.10% carbon, 18.00-21.00% chromium, 12.00-15.00% cobalt, 3.50-5.00% molybdenum, 1.20-1.60% aluminum, 2.75-3.25% titanium, 0.02-0.08% zirconium, 0.003-0.010% boron, 0.10% max manganese, 0.15% max silicon, 0.015% max phosphorus, 0.015% max sulfur, 2.00% max iron, 0.10% max copper, 0.0005% max lead, 0.00003% max bismuth, 0.0003% max selenium, and the balance nickel. Nevertheless, there remains a need in the art to develop higher strength, higher temperature capability alloys, particularly for fastener components and other parts for higher temperature service, thus making it possible to construct turbine engines and other equipment for higher operating temperatures and greater efficiency than heretofore possible. Although manufacturing process improvements, such as the method described in the aforementioned U.S. Patent No. 4,908,069, may be able to provide useful enhancement of the properties of certain alloys, modification of the alloy chemistry tends to provide a much more commercially desirable and useful means to achieve the blend of properties desired for fastener components and other parts at higher service temperatures. Accordingly, the work which led to the present invention was undertaken to develop fastener materials primarily by means of increased alloying rather than process innovation. Selected properties generally considered important for fastener applications include: component produceability, tensile strength, stress- and creep-rupture strength, corrosion resistance, fatigue strength, shear strength and thermal expansion coefficient. An alloy designer can attempt to improve one or two of these design properties by adjusting the compositional balance of known alloys. However, despite the teachings of the prior art, it is still not possible for those skilled in the art to predict with any significant degree of accuracy the physical and mechanical properties that will be displayed by certain concentrations of known elements used in combination to form such alloys. Furthermore, it is extremely difficult to improve more than one or two of the materials' engineering properties without significantly or even severely compromising the remaining desired characteristics. Alloy design is a procedure of compromise which attempts to achieve the best overall mix of properties to satisfy the various requirements of component design. Rarely is any one property maximized without compromising another property. Rather, through development of a critically balanced chemistry and proper processing to produce the component, the best compromise among the desired properties is achieved. The unique alloys of the present invention provide an excellent blend of the properties necessary for use in producing fastener components and other parts for higher temperature service, such as up to about 760°C (1400°F). SUMMARY OF THE INVENTION It is an object of the present invention to provide nickel-cobalt based alloy compositions and articles made therefrom having unique blends of desirable properties. It is a further object of the present invention to provide nickel-cobalt based alloys and articles made therefrom for use in turbine engines and other equipment under high stress, high temperature conditions, such as up to about 760°C (1400°F). These objects are achieved with a high strength nickel-cobalt based alloy having the features of claim 1, an article and a high-strength fastener according to claim 8 and 10, respectively. Articles for use at elevated temperatures can be suitably made from the alloys of this invention. The article can be a component for turbine engines or other equipment subjected to elevated operating temperatures and, more particularly, the component can be a fastener for use in such engines and equipment. The nickel-cobalt based alloy compositions of this invention have critically balanced alloy chemistries which result in unique blends of desirable properties at elevated temperatures. These properties include: component produceability, particularly for fastener components; very good tensile strength, excellent stress-rupture strength, very good corrosion resistance, very good fatigue strength, very good shear strength, excellent creep-rupture strength up to about 816°C (1500°F) and a desirable thermal expansion coefficient. The above-mentioned and other objects and advantages of the present invention will be apparent to those skilled in the art upon reference to the following detailed description of the preferred embodiments. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a Larson Miller stress-rupture plot comparing results from CMBA-6 and CMBA-7 alloy samples of the present invention to those of prior art Waspaloy and MP210 alloys. FIG. 2 is a Larson Miller stress-rupture plot comparing results from CMBA-7 alloy samples of the present invention to those of prior art Waspaloy and Rene 95 alloys. FIG. 3 is a Larson Miller stress-rupture plot comparing results from CMBA-7 alloy samples of the present invention to those of prior art MERL 76 alloy. FIG. 4 is a photomicrograph (Etchant: 150 ml HCl + 100 ml ethyl alcohol + 13 g cupric chloride) at 400X magnification of sample CMBA-6 of the present invention, which has a fully worked and aged bar microstructure that has been hot extruded, hot rolled, cold swaged and aged 10 hours at 719°C (1325°F). FIG. 5 is a photomicrograph (Etchant: 150 ml HC1 + 100 ml ethyl alcohol + 13 g cupric chloride) at 400X magnification of sample CMBA-7 of the present invention, which has a fully worked and aged bar microstructure that has been hot extruded, hot rolled, cold swaged and aged 10 hours at 719°C (1325°F). FIG. 6 is a photomicrograph (Etchant: 150 ml HCl + 100 ml ethyl alcohol + 13 g cupric chloride) at 1000X magnification of a creep-rupture specimen microstructure of a CMBA-7 sample of the present invention, produced under 760°C/413.7N/mm 2 (1400°F/60.0 ksi) test condition with a rupture life of 994.4 hours. FIG. 7 is a scanning electron photomicrograph (Etchant: 150 ml HCl + 100 ml ethyl alcohol + 13 g cupric chloride) at 5000X magnification of the fracture section of a creep-rupture specimen of a CMBA-7 sample of the present invention, produced under 760°C/413.7N/mm 2 (1400°F/60.0 ksi) test condition with a rupture life of 994.4 hours. FIG. 8 is a scanning electron photomicrograph (Etchant: 150 ml HC1 + 100 ml ethyl alcohol + 13 g cupric chloride) at 10,000X magnification of the fracture section of a creep-rupture specimen of a CMBA-7 sample of the present invention, produced under 760°C/413.7N/mm 2 (1400°F/60.0 ksi) test condition with a rupture life of 994.4 hours. DESCRIPTION OF THE PREFERRED EMBODIMENTS The nickel-cobalt based alloys of the present invention are given in claim 1, and preferred embodiments in dependent claims 2-7. These alloy compositions have critically balanced alloy chemistries which result in unique blends of desirable properties, which are particularly suitable for use in producing fastener components. These properties include increased thermal stability, microstructural stability, and stress- and creep-rupture strength at elevated temperatures, particularly up to about 760°C (1400°F), relative to prior art nickel and nickel-cobalt based alloys which are used to produce fastener components. Major factors which restrict the higher temperature strength of prior art alloys, such as the MP159 alloy, include the instability of the solid solution and gamma prime strengthening phases at higher temperature. Prolonged exposure at elevated temperatures in such materials can result in the dissolution of desired strengtheners and reprecipitation of non-cubic, ductility- and strength-deterring phases. The HCP to FCC transus temperature in these prior art alloys and the thermal stability of the strengthening phases can be improved by alloy additions. The elements which normally form the gamma-prime phase are nickel, titanium, aluminum, niobium, vanadium and tantalum, while the matrix is dominated by nickel, chromium, cobalt, molybdenum and tungsten. The alloys of the present invention are balanced with such elements to provide relatively high HCP/FCC transus temperature, microstructural stability and stress/creep-rupture strength. The alloys of the present invention have a tantalum content of 3.8 percent to 5.0 percent by weight, and the tungsten content is from 1.8 percent to 3.0 percent by weight. In the present alloys, tungsten and tantalum may contribute to increasing the FCC/HCP transus temperature. Concurrently, these elements provide significant solid solution strengthening to the alloys due to their relatively large atomic diameter and, therefore, are important additions for strength retention while potentially allowing an increase in ductility through lower cold work levels. The lower cold work levels are possible since the alloys of the present invention do not depend exclusively upon cold work for strength attainment. This invention's alloys must also have at least one gamma-prime forming element selected from the group consisting of aluminum, titanium, niobium, tantalum and vanadium. The aluminum content is 0.9 - 1.1 percent by weight, and the titanium content is 1.9 - 4.0 percent by weight. Advantageously, aluminum is present in an amount of 0.9 percent to 1.1 percent by weight, and titanium is present in an amount of 1.9 percent to 4.0 percent by weight. The aluminum and titanium additions in these compositions promote gamma-prime formation. Furthermore, it is believed that the strength and volume fraction of the gamma-prime phase is increased through the additions of tantalum and niobium to these alloys, thereby increasing the alloys' strength. The elements aluminum, titanium and tantalum are also effective in these alloys toward providing improved environmental properties, such as resistance to hot corrosion and oxidation. The niobium is present in an amount of 0.9 percent to 1.3 percent by weight. The amount of tantalum that can be added to these alloys is higher than niobium since, besides partitioning to the gamma prime, tantalum contributes favorably to the alloys' matrix. It is a more effective strengthener than niobium due to its greater atomic diameter. Gamma-prime phase formation is promoted in these alloys since it assists the attainment of the high strength. Additionally, a significant volume fraction of gamma prime is desired since it may assist in the materials' response to various types of processing, such as methods which involve aging first, then cold working, followed by a further aging treatment; such methods potentially lowering the amount of cold work required for strength attainment in this type of material. The vanadium content in these compositions is 0 to 0.01 percent by weight. The alloys of this invention have a carbon content of 0.005 - 0.03 percent by weight. Carbon is added to these alloys since it assists with melt deoxidation during the VIM production process, and may contribute to grain boundary strength in these alloys. Additionally, the boron content is 0.01 percent to 0.02 percent by weight. Boron is added to these alloys within the specified range in order to improve grain boundary strength. The amount of chromium in the alloys of the present invention is 13.0 percent to 17.5 percent by weight Chromium provides corrosion resistance to these alloys, although it may also assist with the alloys' resistance to oxidation. Furthermore, the molybdenum content is 2.7 percent to 4.0 percent by weight. The addition of molybdenum to these compositions is a means of improving the strength of the alloys. Moreover, the zirconium content is 0 to 0.02 percent by weight. Zirconium also improves grain boundary strength in these alloys. The cobalt content is 24.5 to 34.0 percent by weight. Cobalt assists in providing a stable multiphase structure and possibly corrosion resistance to these alloys. The balance of this invention's alloy compositions is comprised of nickel and small amounts of incidental impurities. Generally, these incidental impurities are entrained from the industrial process of production, and they should be kept to the least amount possible in the compositions so that they do not affect the advantageous aspects of the alloys. For example, these incidental impurities do not exceed: 0.025 percent by weight silicon, 0.01 percent by weight manganese, 0.1 percent by weight iron, 0.01 percent by weight copper, 0.01 percent by weight phosphorus, 0.002 percent by weight sulfur, 0.001 percent by weight nitrogen and 0.001 percent by weight oxygen. Not only do the alloys of this invention have a composition within the above specified ranges, but they also have a phasial stability number N v3B less than 2.50. As can be appreciated by those skilled in the art, N v3B is defined by the PWA N-35 method of nickel-based alloy electron vacancy TCP phase control factor calculation. This calculation is as follows: EQUATION 1 Conversion for weight percent to atomic percent: Atomic percent of element i, designated P i P i = W i / A i Σ W i / A i × 100 where: W i = weight percent of element i A i = atomic weight of element i EQUATION 2 Calculation for the amount of each element present in the continuous matrix phase: Element Atomic Amount R i in Matrix Phase Cr R Cr = 0.97P Cr - 0.375P B - 1.75P C Ni R Ni = P Ni + 0.525P B - 3(P Al + 0.03P Cr + P Ti - 0.5P C + 0.5P V + P Ta + P Nb Ti, Al, B, C, Ta, Nb R i = 0 V R V = 0.5P V W R W = P W - 0.167 P C P W P Mo + P W Mo R Mo = P Mo - 0.75 P B - 0.167 P C P Mo P Mo + P W EQUATION 3 Calculation of N v3B using atomic factors from Equations 1 and 2 above: N i i = R i Σ R i then N v3B = Σ N i i ( N v ) i where: i = each individual element in turn. N i i = the atomic factor of each element in matrix. (N v )i = the electron vacancy No. of each respective element. This calculation is exemplified in detail in a technical paper entitled "PHACOMP Revisited", by H. J. Murphy, C. T. Sims and A. M. Beltran, published in Volume 1 of International Symposium on Structural Stability in Superalloys (1968). As can be appreciated by those skilled in the art, the phasial stability number for the alloys of this invention is critical and must be less than the stated maximum to provide a stable microstructure and capability for the desired properties under high temperature conditions. The phasial stability number can be determined empirically, once the practitioner skilled in the art is in possession of the present subject matter. The alloys of the present invention exhibit increased thermal stability and microstructural stability, such as resistance to formation of undesirable TCP phases, at elevated temperatures up to about 760°C (1400°F). Furthermore, this invention provides alloy compositions having unique blends of desirable properties. These properties include: component produceability, particularly for fastener components; very good tensile strength, excellent stress-rupture life, very good corrosion resistance, very good fatigue strength, very good shear strength, a desirable thermal expansion coefficient, and excellent resistance to creep under high stress, high temperature conditions up to about 816°C (1500°F). One embodiment of this invention has the capability of withstanding 199.9N/mm 2 (29 ksi) stress at 704°C (1300°F) for 1000 hours before exhibiting 0.1% creep deformation and 310.3N/mm 2 (45 ksi) stress at 704°C (1300°F) for 1000 hours before exhibiting 0.2% creep deformation. The alloys have a multiphase structure with a platelet phase and a gamma prime phase dispersed in a face centered cubic matrix, which is believed to be a factor in providing the improved higher temperature properties of these alloys. These alloys are also substantially free of embrittling phases. Nevertheless, as noted above, the alloys of this invention have precise compositions with only small permissible variations in any one element if the unique blend of properties is to be maintained. This invention's alloys can be used to suitably make articles for use at elevated temperatures, particularly up to about 760°C (1400°F). The article can be a component for turbine engines or other equipment subjected to elevated operating temperatures. However, the alloy compositions of this invention are particularly useful in making high strength fasteners having increased thermal stability and microstructural stability at elevated temperatures up to about 760°C (1400°F), while maintaining extremely good mechanical strength and corrosion resistance. Examples of fastener parts which can be suitably made from the alloys of this invention include bolts, screws, nuts, rivets, pins and collars. These alloys can be used to produce a fastener having an increased resistance to creep under high stress, high temperature conditions up to about 816°C (1500°F), as well as a stress- rupture life at 704°C (1300°F)/689,5 N/mm 2 (100 Ksi) condition greater than 150 hours, which are considered important alloy properties that are highly desirable when producing fasteners for use in turbine engines and other equipment subjected to elevated operating temperatures. The alloy compositions of this invention are suitably prepared and melted by any appropriate technique known in the art, such as conventional ingot metallurgy techniques or by powder metallurgy techniques. Thus, the alloys can be first melted, suitably by vacuum induction melting (VIM), under appropriate conditions, and then cast as an ingot. After casting as ingots, the alloys are preferably homogenized and then hot worked into billets or other forms suitable for subsequent working. However, evaluations of the present invention undertaken with larger diameter VIM product revealed that ingot microstructural variation and elemental segregation may adversely affect the yield of hot reduced product for alloys of this invention. For this reason, it may be desirable to vacuum arc remelt (VAR) or electroslag remelt (ESR) the alloys before they are worked and aged. ESR and VAR are two types of consumable electrode melting processes that are well known in the art. In these processes, a VIM ingot (electrode) is progressively melted from one end to the other with the resulting molten pool of metal resolidified under controlled conditions, producing an ingot with reduced elemental segregation and improved microstructure as compared to the starting VIM electrode. In the VAR process, the melting and resolidification may occur in vacuum which may reduce the level of high vapor pressure tramp elements in the melt. ESR is carried out using a molten refining slag layer between the electrode and the resolidifying ingot. As molten metal droplets descend from the electrode through the molten slag, compositional refining and removal of impurities can occur prior to resolidification in the ingot. The improved microstructure and reduction in elemental segregation imparted to the resulting ingot by either of these consumable electrode melting processes results in improved response to subsequent heat treating and hot working operations. Alternatively, the molten alloy can be impinged by gas jet or otherwise dispersed as small droplets to form powders. Powdered alloys of this sort can then be densified into a desired shape according to techniques known in powder metallurgy. Also, spray casting techniques known in the art can be utilized. The alloys of the present invention are advantageously worked to achieve a reduction in cross-section of at least 5 percent. In a preferred embodiment, the alloy is cold worked to achieve a reduction in cross-section of from about 10% to 40%, although higher levels of cold work may be used with some loss of functionality. As used herein, the term "cold working" means deformation at a temperature (below the FCC/HCP transus temperature) which will induce the transformation of a portion of the metastable FCC matrix into the platelet phase. Also as used herein, the term "hot working" means deformation at a temperature above the FCC/HCP transus temperature. The alloys can be aged after cold working. For example, the alloys can be aged for about 1 to about 50 hours after cold working. The alloys are advantageously aged at a temperature of from about 427°C (800°F) to about 760° (1400°F) for about 1 hour to about 50 hours after cold working. Alternatively, the alloys can be first aged, cold worked to achieve a reduction in cross-section of at least 5%, and then aged again. Advantageously, the alloys are aged at a temperature of from about 649°C (1200°F) to about 899°C (1650°F) for about 1 hour to about 200 hours, cold worked to achieve a reduction in cross-section of about 10% to 40% and then aged again at a temperature of from about 427°C (800°F) to about 760°C (1400°F) for about 1 hour to about 50 hours. Following aging, the alloys may be air-cooled. A process for producing nickel-cobalt based alloys having the compositions as described in claim 1 by forming a melt comprising the elements with the ranges given by claim 1, the alloy having a phasial stability number N v3B less than 2.50. (b) cooling the melt to form solid alloy material; (c) hot working the solid alloy material to reduce the material to a size suitable for cold working; (d) cold working the alloy material to achieve a reduction in cross-section of at least 5%; and (e) aging the cold-worked alloy material at a temperature of from about 427°C (800°F) to about 760°C (1400°F) for about 1 to about 50 hours. As noted above, the alloys can be vacuum arc remelted or electroslag remelted before being worked and aged. The alloys can also be aged first, cold worked to achieve the necessary reduction in cross-section, and then aged again. For example, the alloys can first be aged at a temperature of from about 649°C (1200°F) to about 899°C (1650°F) for about 1 hour to about 200 hours before being cold worked to achieve a reduction in cross-section of at least 5%. However, as can be appreciated by those skilled in the art, the optimum temperatures and times for cold working and aging in all of the above processing steps depends on the precise composition of the alloy. Additionally, the cold worked alloy can be air-cooled after aging. The process of this invention can be suitably used to make alloys for production of fasteners. In order to more clearly illustrate this invention, the examples set forth below are presented. The following examples are included as being illustrations of the invention and its relation to other alloys and articles, and should not be construed as limiting the scope thereof. Four different alloy processing methods were undertaken during the evaluation to determine the compositions of this invention. Generally, the processing methods employed, corresponding to Examples 1, 2, 3, 4 and 5 set forth below, were as follows: 1. VIM + Hot Extrusion + Hot Roll + Cold Work (swaging) 2. VIM + Hot Extrusion + Hot Roll + Cold Draw 3. VIM + ESR + Hot Roll + Cold Roll 4. VIM + ESR + Hot Roll + Cold Draw 5. VIM + ESR + Hot Roll + Cold Draw EXAMPLE 1 The experimental development work which resulted in the compositions of the present invention began with the definition of two alloy systems, designated CMBA-6 and CMBA-7. Follow-on work defined a third alloy system, designated CMBA-8. The developmental compositions were designed to exhibit multiphase-type reaction, i.e., partial transformation with cold work of the metastable FCC matrix to its lower temperature HCP structure, while also utilizing more conventional strengthening mechanisms. Initially, 5.08 cm (two inch) diameter bars of the CMBA-6 and CMBA-7 alloy compositions were produced. The melting was done in a vacuum furnace, which operated with an argon backfill. The aim chemistries and actual cast ingot chemistries for the CMBA-6 and CMBA-7 alloy samples are presented in Table 1 below. Similarly, the aim chemistry and actual cast ingot chemistry for the subsequently produced CMBA-8 alloy sample is also presented in Table 1. It is believed that fairly good correlation of alloy aim chemistry to actual cast ingot content prevailed. Additionally, standard N v3B calculations (discussed above) were performed to assist with respective alloy phasial stability predictions, with the results also presented in Table 1 below. Weight % CMBA-6 CMBA-7 CMBA-8 Element Aim Cast Ingot Aim Cast Ingot Aim Cast Ingot C .015 .010 .105 .020 .015 .024 Si LAP <.05 LAP <.05 LAP .004 Mn LAP <.05 LAP <.05 LAP .001 B .015 .018 .015 .016 .015 .014 Nb 1.1 1.2 1.1 1.1 1.1 1.1 Cr 17.0 16.9 17.0 17.0 14.5 14.6 Mo 3.0 2.9 3.5 3.4 3.5 3.5 Co 25.0 24.1 30.0 28.4 33.0 33.1 Al 1.0 1.06 1.0 1.03 1.0 .96 Ti 2.0 1.98 3.0 3.1 3.5 3.7 Ta 4.0 3.9 4.0 3.9 4.5 4.3 W 2.0 1.9 2.0 1.9 2.5 2.4 V LAP <.01 LAP <.01 LAP <.01 Ni BASE BASE BASE BASE BASE BASE Fe LAP <.05 LAP <.10 LAP <.05 Cu LAP <.02 LAP <.02 LAP .003 S ppm LAP 7 LAP 6 LAP 16 [N] ppm LAP 25 LAP 100 LAP 6 [O] ppm LAP 36 LAP 40 LAP 28 N v3B (PWA N-35) 2.23 2.21 2.45 2.43 2.45 2.46 LAP - low as possible The CMBA-6 and CMBA-7 alloys were homogenized as follows: the CMBA-6 sample was soaked at 1177°C (2150°F) for approximately 27 hours, and the CMBA-7 sample was soaked at 1218°C (2225°F) for approximately 46 hours. The CMBA-8 ingot, which was subsequently produced, was used to develop the alloy solution/homogenization treatment utilized in the Example 3 below. Following homogenization, the CMBA-6 and CMBA-7 alloys were surface cleaned to remove oxide scale, and subsequently canned with stainless steel in preparation for extrusion. The test bars were extruded at 1149°C (2100°F), at a reduction ratio of 2.56:1, to 3.175 cm (1.25 inch) diameter bar. Subsequent to hot extrusion, the samples were subjected to hot rolling and cold swaging. The 35.56 cm (14 inch) long, 3.175 cm (1.25 inch) diameter canned bars were hot reduced at 1163°C (2125°F) to a nominal 1.52 cm (0.60 inch) diameter through a total of 14 passes on a 35.56 cm (14 inch) mill. Five swage passes at room temperature resulted in cold work level ranging 25-34%, with reduction to diameter of 0.305-0.762 mm (0.012-0.030 inches) per pass. Most of these test materials were aged at 719°C (1325°F)/10 Hr./AC (air-cooled) test condition following cold work. Other test samples were aged for 20 hours at temperatures in the 719-816°C (1325-1500°F) range, and limited room temperature and elevated temperature tensile tests were undertaken. The aged specimens were machined/ground, and then tensile, stress-rupture and creep-rupture tested; all in accordance with standard ASTM procedures. The results of tensile tests performed at room temperature (RT), 482°C (900°F), 593°C (1100°F), 649°C (1200°F) and 704°C (1300°F) with CMBA-6 and CMBA-7 alloy samples are presented below in Tables 2 and 3 respectively. LONGITUDINAL TENSILE PROPERTY COMPARISON CMBA-6 vs. WASPALOY Test Temp (°F/°C) Alloy 0.2% Yield N/mm 2 UTS N/mm 2 ELONG (%) RA (%) RT WASPALOY 896.3 1310.0 22.0 25.0 CMBA-6 1903.6 1963.6 5.5 18.5 900/482 CMBA-6 1636.1 1676.8 6.1 23.9 1100/593 WASPALOY 810.1 1223.8 18.5 27.5 CMBA-6 1609.9 1647.2 5.8 20.8 1200/649 WASPALOY 792.9 1206.6 15.0 30.0 CMBA-6 1568.6 1625.8 6.1 22.4 1300/704 WASPALOY 775.7 1051.5 21.0 40.0 CMBA-6 1475.5 1565.1 4.6 14.5 Notes: · CMBA 6 -- 27% Cold Worked Bar Specimens. · WASPALOY -- Forged and Fully Heat Treated to Rockwell C38 (Method "B"); Source: Engineering Alloys Digest, Inc., Upper Montclair, New Jersey. LONGITUDINAL TENSILE PROPERTY COMPARISON CMBA-7 vs. WASPALOY Test Temp (°F/°C) Alloy 0.2% Yield N/mm 2 UTS N/mm 2 ELONG (%) RA (%) RT WASPALOY 896.3 1310.0 22.0 25.0 CMBA-7 2042.9 2102.2 2.3 5.6 900/482 CMBA-7 1777.5 1831.9 6.3 16.1 1100/593 WASPALOY 810.1 1223.8 18.5 27.5 CMBA-7 1711.3 1805.7 3.8 13.1 1200/649 WASPALOY 792.9 1206.6 15.0 30.0 CMBA-7 1739.5 1785.7 6.3 13.1 1300/704 WASPALOY 775.7 1051.5 21.0 40.0 CMBA-7 1649.9 1720.9 5.3 14.3 Notes: · CMBA 7 -- Approximately 30% Cold Worked Bar Specimens. · WASPALOY -- Forged and Fully Heat Treated to Rockwell C38 (Method "B"); Source: Engineering Alloys Digest, Inc., Upper Montclair, New Jersey. The CMBA-6 tensile test results presented in Table 2 are compared to typical Waspaloy properties. In general, these results indicate that CMBA-6 provides much higher tensile strength than Waspaloy, but with lower ductility. Similarly, the CMBA-7 tensile test results presented in Table 3 illustrate the alloy provides even greater advantage over Waspaloy, but again, with considerably lower ductility. Test results from a study of the effects of aging temperature variation on the CMBA-7 alloy are presented in Table 4 below. CMBA-7 RT LONGITUDINAL TENSILE STRENGTH RESULTS OF AGING TEMPERATURE VARIATION Age Condition 0.2% Yield N/mm 2 UTS N/mm 2 ELONG (%) RA (%) 719°C/20 hrs. 2093.9 2136.7 2.3 6.8 732°C/20 hrs. 2042.9 2111.2 2.7 6.8 746°C/20 hrs. 2068.4 2119.4 2.4 8.0 760°C/20 hrs. 2014.6 2073.9 2.1 5.7 788°C/20 hrs. 1948.5 2032.6 1.5 3.6 816°C/20 hrs. 1867.8 1944.3 2.3 7.0 Notes: Round bar test specimens, approximately 30% cold work The results presented in Table 4 show that increasing the CMBA-7 aging temperature (above 719° C (1325°F)) did not improve the alloy's RT tensile ductility. The results of stress- and creep-rupture tests performed with CMBA-6 and CMBA-7 alloy samples are presented in Table 5 below. ELEVATED TEMPERATURE STRESS AND CREEP-RUPTURE DATA CMBA-6 AND CMBA-7 ALLOYS Alloy Test Condition Rupture Time Hours % EL (4D) RA % Final Creep Reading Time in Hours to Reach t, Hours % Deformation 1.0% 2.0% CMBA-6 649°C/1061.8N/mm 2 33.0 --- --- 31.4 0.261 --- --- 649°C/1061.8N/mm 2 205.2 --- --- --- --- --- --- 704°C/741.2N/mm 2 644.4 3.9 4.6 641.3 2.510 362.7 605.0 704°C/551.6N/mm 2 5240.4 4.1 7.0 5238.7 3.066 3095.4 4881.0 732°C/579.2N/mm 2 715.0 3.3 5.7 714.9 2.452 447.4 694.1 760°C/551.6N/mm 2 168.9 2.8 4.4 168.3 2.514 52.0 145.3 760°C/551.6N/mm 2 271.1 4.6 4.4 269.6 3.531 150.4 233.4 788°C/379.2N/mm 2 102.0 4.5 5.8 --- --- --- --- 816°C/344.7N/mm 2 CMBA-7 593°C/1103.2N/mm 2 25554.7 5.0 7.0 --- --- --- --- 649°C/1061.8N/mm 2 6.6 --- --- 5.3 0.215 --- --- 649°C/1061.8N/mm 2 1183.7 4.8 9.4 1179.5 3.018 484.0 946.0 649°C/827.4N/mm 2 14679.5 10.3 16.1 --- 9.058 5360.0 11989.9 649°C/689.5N/mm 2 25618.4 22854.0 --- 704°C/741.2N/mm 2 1523.3 10.3 19.6 1521.0 8.678 564.9 1151.8 704°C/551.6N/mm 2 6725.4 10.3 17.1 6724.6 9.828 2510.0 5055.0 732°C/579.2N/mm 2 1154.9 9.3 16.4 1154.9 9.015 437.1 831.9 760°C/551.6N/mm 2 304.9 11.5 15.1 304.7 10.901 72.6 181.0 760°C/413.7N/mm 2 994.4 8.2 14.5 993.0 7.479 423.5 710.1 788°C/379.2N/mm 2 277.9 8.0 10.4 276.1 7.165 107.0 183.0 788°C/379.2N/mm 2 190.9 6.1 8.2 187.3 4.267 65.9 132.9 816°C/349.7N/mm 2 60.6 5.3 3.8 --- --- --- --- 732°C/585.4N/mm 2 571.6 --- --- --- --- --- --- Notes: · Test bar prep: Solution, hot extrude, hot roll, approx. 25% cold work, then aged. · Test specimens machined/ground for testing. · Predominantly 4.064 mm (0.160") dia. gage specimens. The test results presented in Table 5 indicate that the CMBA-7 composition exhibits greater creep-rupture strength than the CMBA-6 composition. A specific example of this is provided in Table 5 wherein comparison of time to 1.0% and 2.0% creep for the two alloys tested at the 704°C/741.2 N/mm 2 (1300°F/107.5 ksi) condition shows the CMBA-7 sample creeping at a significantly lower rate. The test results presented in Table 5 further indicate that the CMBA-7 composition also provides greater rupture strength and rupture ductility than the CMBA-6 composition. Additionally, some of the rupture results tabulated are graphically represented in Figure 1 where a Larson Miller stress-rupture plot provides a comparison of the alloys' capabilities. For a running stress of 741.2 N/mm 2 (107.5 ksi), it is calculated that the CMBA-7 alloy provides a 12°C (21°F) metal temperature advantage relative to CMBA-6 alloy. Similarly, a 9°C (16°F) advantage is indicated at 551.6 N/mm 2 (80.0 ksi.) Figure 1 also plots the elevated temperature rupture capability of Waspaloy and MP 210 (the alloy disclosed in the aforementioned U.S. Patent No. 4,795,504). It is apparent that for the 689.5 N/mm 2 (100 ksi) stress level, CMBA-7 alloy provides approximate respective metal temperature advantages of 39°C (71°F) over MP210 alloy and 71°C (127°F) over Waspaloy. Similarly, for 551.6 N/mm 2 (80.0 ksi) stressed exposure, the alloy exhibits approximately 36°C (64°F) advantage vs. MP210 alloy and 52°C (94°F) advantage relative to Waspaloy. Figure 2 is another Larson Miller stress-rupture plot comparing the CMBA-7 alloy to Waspaloy and Rene 95 alloy (a product of the General Electric Company). As illustrated in Figure 2, for an 551.6 N/mm 2 (80.0 ksi) operating stress, CMBA-7 alloy provides approximately 32°C (57°F) greater metal temperature capability than Rene 95 alloy. Furthermore, comparison to Waspaloy at 413.7 N/mm 2 (60 ksi) indicates that the CMBA-7 alloy provides an additional approximate 36°C (64°F) capability. Similarly, Figure 3 is a Larson Miller stress-rupture plot comparing the CMBA-7 alloy's rupture strength to the MERL 76 alloy (a product of the United Technologies Corporation). The Figure illustrates that for a 413.7 N/mm 2 (60 ksi) stress level, the CMBA-7 alloy provides an approximate 23°C (41°F) metal temperature advantage relative to MERL 76 alloy. Bar samples (9.525 mm (.375") diameter x 7.62 cm (3") long) of CMBA-6 and CMBA-7 alloys have been exposed to a 5% salt fog environment per ASTM B117 for approximately 4 years with no visible signs of corrosion. Photomicrographs of CMBA-6 and CMBA-7 alloy samples, which were prepared with an optical metallograph, are presented in Figures 4-6. Also, scanning electron microscope generated micrographs of CMBA-7 alloy samples are presented in Figures 7 and 8. FIG. 4 is a photomicrograph at 400X magnification of a CMBA-6 sample of the present invention, which has a fully worked and aged bar microstructure that has been hot extruded, hot rolled, cold swaged and aged 10 hours at 719°C (1325°F). FIG. 5 is a photomicrograph at 400X magnification of a CMBA-7 sample of the present invention, which has a fully worked and aged bar microstructure that has been hot extruded, hot rolled, cold swaged and aged 10 hours at 719°C (1325°F). FIG. 6 is a photomicrograph at 1000X magnification of a creep-rupture specimen microstructure of a CMBA-7 sample of the present invention, produced under 760°C/413.7 N/mm 2 (1400°F/60.0) ksi test condition with a rupture life of 994.4 hours. FIG. 7 is a scanning electron photomicrograph at 5000X magnification of the fracture section of a creep-rupture specimen of a CMBA-7 sample of the present invention, produced under 760°C/413.7 N/mm 2 (1400°F/60.0) ksi test condition with a rupture life of 994.4 hours. FIG. 8 is a scanning electron photomicrograph at 10,000X magnification of the fracture section of a creep-rupture specimen of a CMBA-7 sample of the present invention, produced under 760°C/413.7 N/mm 2 (1400°F/60.0) ksi test condition with a rupture life of 994.4 hours. EXAMPLE 2 7.62 cm (3") diameter and larger diameter VIM product was produced utilizing both laboratory and production-type processes. Table 6 below presents the chemistry of the CMBA-6 heats produced in both process types. Similarly, Table 7 below details the chemistry analyses for nine CMBA-7 VIM heats produced, while Table 8 below presents the chemistry detail for eight CMBA-8 VIM heats produced. CMBA-6 ALLOY HEAT CHEMISTRIES Element Heat No. AE 5 Heat No. AE 28 Heat No. VF 687 Heat No. VF 726 Heat No. VF 738 Heat No. VF 755 Heat No. VF 790 Heat No. W 584 C .012 .014 .013 .016 .014 .014 .014 .013 Si .013 .014 .014 <.02 <.03 <.03 .015 <.02 Mn .002 <.03 .001 <.02 <.03 <.03 .001 <.01 S ppm 5 9 6 10 6 5 5 12 Cr 17.3 17.3 17.3 16.9 17.1 17.0 16.8 16.9 Co 25.4 25.2 24.9 24.9 25.0 25.0 24.9 25.0 Mo 3.2 3.1 3.0 3.0 3.0 3.0 3.0 3.0 W 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Ta 3.9 3.9 4.0 4.0 4.0 4.0 4.0 4.0 Nb 1.2 1.16 1.15 1.14 1.11 1.12 1.1 1.1 Al 1.00 1.01 1.03 1.03 1.01 1.08 .99 1.07 Ti 2.06 2.0 2.02 2.08 2.06 2.17 2.19 2.13 Zr <.001 <.001 <.001 <.003 <.005 <.010 <.002 <.005 B .018 .020 .023 .014 .018 .013 .015 .018 Fe .04 .03 .029 <.03 <.05 .09 .05 .049 Cu <.01 <.05 <.001 <.02 <.01 <.02 <.005 <.005 Ni BAL BAL BAL BAL BAL BAL BAL BAL V --- --- <.005 <.05 <.02 <.05 <.005 <.005 P <.005 <.005 <.015 <.015 <.015 <.015 <.015 <.015 [N] ppm 4 8 2 6 17 4 4 3 [O] ppm 6 18 2 4 3 4 3 1 Pb ppm --- --- <.5 <.5 < 1 <.5 <.5 <.5 Ag ppm --- --- <.2 <.2 <.2 <.2 <.2 <.2 Bi ppm --- --- <.2 <.2 <.2 <.2 <.2 <.2 Se ppm --- --- <.5 <.5 <.5 <.5 <.5 <.5 Te ppm --- --- <.2 <.2 <.2 <.2 <.2 <.2 Tl ppm --- --- <.2 <.2 <.2 <.2 <.2 <.2 Sn ppm --- --- < 5 < 5 < 5 < 5 < 5 < 5 Sb ppm --- --- < 1 < 1 < 1 < 1 < 1 < 1 As ppm --- --- < 1 < 1 < 1 < 1 < 1 < 1 Zn ppm --- --- < 1 < 1 < 1 < 3 < 2 < 1 Nv3B (PWA N-35) 2.27 2.26 2.26 2.24 2.24 2.27 2.24 2.25 CMBA-7 ALLOY HEAT CHEMISTRIES Element Heat No. AE 6 Heat No. AE 29 Heat No. VF 688 Heat No. VF 727 Heat No. VF 739 Heat No. VF 756 Heat No. VF 791 Heat No. VF 803 Heat No. VF 926 C .010 .016 .015 .013 .011 .014 .010 .014 .013 Si .013 .011 .010 <.02 <.03 <.03 <.03 <.03 <.02 Mn .002 <.03 .001 <.02 <.03 <.03 <.02 <.03 <.02 S ppm 5 8 7 8 6 7 7 4 7 Cr 17.0 17.2 17.2 16.7 16.9 17.1 16.8 16.9 16.8 Co 29.6 29.8 29.9 30.4 30.1 30.2 29.7 30.1 30.0 Mo 3.5 3.5 3.5 3.4 3.5 3.5 3.5 3.4 3.5 W 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Ta 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Nb 1.2 1.2 1.22 1.17 1.15 1.15 1.14 1.15 1.17 Al .99 1.01 1.03 1.04 1.00 1.06 1.02 1.06 1.04 Ti 3.00 2.97 2.99 3.00 2.97 3.09 3.09 3.12 3.10 Zr <.001 <.001 <.001 <.01 <.005 <.01 <.01 <.01 <.01 B .016 .017 .021 .019 .014 .020 .019 .017 .018 Fe .04 .04 .02 <.05 <.05 <.10 <.10 <.10 .05 Cu <.01 <.05 <.001 <.01 <.01 <.01 <.01 <.01 <.01 Ni BAL BAL BAL BAL BAL BAL BAL BAL BAL V --- --- <.005 <.05 <.01 <.05 <.05 <.01 <.05 P <.005 <.005 <.015 <.015 <.015 <.015 <.015 <.015 <.015 [N] ppm 5 6 3 7 12 5 5 40 21 [O] ppm 4 27 4 5 5 4 6 1 3 Pb ppm --- --- <.5 <.5 < 1 <.5 <.5 <.5 <.5 Ag ppm --- --- <.2 <.2 <.2 <.2 <.2 <.2 <.2 Bi ppm --- --- <.2 <.2 <.2 <.2 <.2 <.2 <.2 Se ppm --- --- <.5 <.5 <.5 <.5 <.5 <.5 <.5 Te ppm --- --- <.2 <.2 <.2 <.2 <.2 <.2 <.2 Tl ppm --- --- <.2 <.2 <.2 <.2 <.2 <.2 <.2 Sn ppm --- --- < 5 < 5 < 5 < 5 < 5 < 5 < 5 Sb ppm --- --- < 1 < 1 < 1 < 1 < 1 < 1 < 1 As ppm --- --- < 1 < 1 < 1 < 1 < 1 < 1 < 1 Zn ppm --- --- < 1 < 2 < 1 < 2 < 1 < 1 < 1 Nv3B (PWA N-35) 2.46 2.47 2.48 2.45 2.45 2.50 2.46 2.48 2.47 CMBA-8 ALLOY HEAT CHEMISTRIES Element Heat No. AE 7 Heat No. AE 30 Heat No. AE 31 Heat No. VF 692 Heat No. VF 728 Heat No. VF 740 Heat No. VF 757 Heat No. VF 792 C .011 .014 .014 .014 .013 .014 .013 .015 Si .008 .011 .011 .009 <.02 <.02 <.03 <.03 Mn .002 <.03 <.03 .002 <.02 <.02 <.03 <.02 S ppm 5 8 8 5 6 6 6 7 Cr 14.4 14.5 14.4 14.4 14.3 14.4 14.4 14.3 Co 32.7 32.8 32.8 32.9 32.9 32.9 33.0 32.9 Mo 3.5 3.5 3.5 3.5 3.6 3.6 3.5 3.5 W 2.4 2.4 2.4 2.6 2.5 2.4 2.5 2.5 Ta 4.4 4.46 4.47 4.5 4.5 4.5 4.4 4.5 Nb 1.1 1.1 1.11 1.10 1.13 1.13 1.13 1.13 Al .95 .97 .96 .99 1.03 .99 1.06 1.05 Ti 3.68 3.64 3.65 3.64 3.69 3.67 3.73 3.75 Zr <.001 <.001 <.001 <.001 <.005 <.005 <.02 <.02 B .014 .014 .013 .016 .017 .017 .018 .018 Fe .04 .04 .04 .03 <.05 <.10 <.10 .03 Cu <.01 <.05 <.05 <.001 <.01 <.01 <.01 <.01 Ni BAL BAL BAL BAL BAL BAL BAL BAL V --- --- --- <.005 <.05 <.05 <.05 <.03 P <.005 <.005 <.005 <.015 <.015 <.005 <.005 <.015 [N] ppm 5 4 6 2 2 2 4 5 [O] ppm 6 18 17 2 6 7 5 6 Pb ppm --- --- --- <.5 <.5 < 1 <.5 <.5 Ag ppm --- --- --- <.2 <.2 <.2 <.2 <.2 Bi ppm --- --- --- <.2 <.2 <.2 <.2 <.2 Se ppm --- --- --- <.5 <.5 <.5 <.5 <.5 Te ppm --- --- --- <.2 <.2 <.2 <.2 <.2 Tl ppm --- --- --- <.2 <.2 <.2 <.2 <.2 Sn ppm --- --- --- < 5 < 5 < 5 < 5 < 5 Sb ppm --- --- --- < 1 < 1 < 1 < 1 < 1 As ppm --- --- --- < 1 < 1 < 1 < 1 < 1 Zn ppm --- --- --- < 2 < 2 < 1 < 3 < 1 Nv3B (PWA N-35) 2.44 2.45 2.45 2.46 2.48 2.47 2.49 2.48 16kg (35 lb.) samples of the CMBA-6 and CMBA-7 alloys were VIM processed to a 9.525 cm (3-3/4") diameter x 17.78 cm (7") long dimension. Samples were homogenize-annealed using a cycle of 10 hours at 1163°C (2125°F) + 40 hours at 1177°C (2150°F). The ingots were canned in 304 stainless steel and extruded to 3.81 cm (1-1/2") diameter at approximately 1149°C (2100°F). After surface conditioning, the extrusions were hot rolled at about 1121°C (2050°F) to a 11.836 mm (.466") diameter bar. Each alloy type was split into two lots. One lot of each alloy was solution treated at 1121°C (2050°F) for 4 hours, aged at 850°C (1562°F) for 10 hours/AC, and then cold drawn to 9.906 mm (.390") diameter for a 30% reduction. The remaining alloy lots were further hot rolled at about 1121°C (2050°F) to 10.973 mm (.423") diameter, solution treated at 1121°C (2050°F) for 4 hours, aged at 850°C (1562°F) for 10 hours/AC and then cold drawn to 9.906 mm (.390") diameter (15% reduction). All lots were given a final age at 719°C (1325°F) for 10 hours/AC. Smooth specimens (6.4 mm (.252") diameter) and threaded studs (5/16-24 x 1.5) were fabricated for testing. Specimen tensile tests were conducted per ASTM E8 and E21 methods, while stud samples were tested in accordance to MIL-STD-1312 test numbers 8 and 18. The test results are presented in Table 9 below. Specimen stress-rupture tests were performed in accordance with ASTM E139 while stud tests were undertaken in accordance with MIL-STD-1312, test number 10. The results of such tests are presented in Table 10 below. CMBA-6 AND CMBA-7 STRESS-RUPTURE DATA Test Condition Stress Rupture Life, hours CMBA-6 (Heats AE 28 & VF 738) CMBA-7 (Heat VF 739) 15% Cold Work 30% Cold Work 15% Cold Work 30% Cold Work A. Specimens 732°C (1350°F)/642,6 N/mm 2 (93.2 Ksi) 0.8 385.7 162.3 300.9 56.8 300.0+ 265.5 136.6 381.1 390.5 732°C (1350°F)/ 470 N/mm 2 (68.2 ksi) 1014.0+ 1103.7+ 1004.5+ 1031.2+ 1003.6+ 390.5 B. Studs 732°C (1350°F)/ 642,6 N/mm 2 (93,2 Ksi) 55.6 167.6 -- -- 35.9 38.5 64.6 732°C (1350°F)/470 N/mm 2 (68.2 ksi) 1709.2 1344.2 1103.7 -- 1174.9+ 1646.5 1413.0 1003.6+ Notes: · Test Article: 6.4 mm (.252") diameter specimens and 5/16-24 x 1.5 studs. · Condition: Solutioned + aged 850°C (1562°F)/10 hours/AC + cold worked as indicated + aged 719°C (1325°F)/10 hours/AC. · Stress for studs based on area at the basic pitch diameter (0.4127 cm 2 (0.06397 in. 2 )). · "+" denotes that the test was terminated prior to failure. The stress-rupture test results presented in Table 10 indicate that the materials exhibit relatively high strength. Tension impact tests were performed with stud samples. The test apparatus employed was the type described in ASTM E23. However, instead of testing notched, rectangular bars, the test utilized threaded fixtures and adaptors which permitted the testing of threaded samples. The apparatus applied an impact load along the longitudinal axis of the respective test pieces, and the energy absorbed by the respective test piece prior to fracture was measured. The results are presented in Table 11 below. CMBA-6 AND CMBA-7 TENSION-IMPACT DATA Test Condition Tension-Impact Strength, J (ft.-lbs.) CMBA-6 (Heats VF 738 & AE 28) CMBA-7 (Heat VF 739) 15% Cold Work 30% Cold Work 15% Cold Work Pre-Exposure 121.6 (89.7) 90.4 (66.7) 135.6 (100.0) Post-Exposure 40.0 (29.5) 36.6 (27.0) 50.2 (37.0) Notes: · Test Article: 5/16-24 x 1.5 studs. · Condition: Solutioned + aged 850°C (1562°F)/10 hours/AC + cold worked as indicated + aged 719°C (1325°F)/10 hours/AC. · Results presented are averaged values. · Stress based on area at the basic pitch diameter (0.4127 cm 2 (0.06397 in. 2 )). Larger diameter CMBA-6, CMBA-7 and CMBA-8 VIM material was processed for hot extrusion and hot rolling reduction, but the effort was not pursued past the hot extrusion reduction since some ingot cracking was experienced. EXAMPLE 3 The materials produced for this example were made in accordance with the aim chemistries indicated in Table 1, except that respective Al and Ti additions were slightly increased due to their expected partial loss during the ESR remelting operation. 7.62 cm (Three-inch) diameter VIM ingot samples (Heats VF 755 and VF 757) were ESR processed into 10.16 cm (four-inch) diameter, 23 k g (50 pound) ingots. A 67-10-10-10-3 slag formulation (67CaF, 10CaO, 10MgO, 10A1 2 O 3 , 3TiO 2 ) was utilized, and it is believed that the alloy chemistries were maintained adequately during the ESR process, although modest silicon and nitrogen pick-up were noted. All test materials were homogenized as follows: CMBA-6 1163°C (2125°F)/4 Hrs. +1177°C (2150°F)/65 Hrs./AC CMBA-7, -8 1177°C (2150°F)/4 Hrs. +1204°C (2200°F)/65 Hrs./AC These materials were then press forged into 7.62 cm (three-inch) square ingots at 1149°C (2100°F)-1177°C (2150°F). The CMBA-6 and CMBA-8 samples were successfully forged further to 3.175 cm (1-1/4 inch) thick slabs, while the CMBA-7 samples cracked. The CMBA-6 and CMBA-8 specimens exhibited minor edge cracking during the subsequent hot rolling reduction to 3.175 mm (1/8 inch) thickness at 1121°C (2050°F)-1149°C (2100°F). Several re-heats were necessary to complete the desired reduction. The materials were cold rolled to reduction ranging 5-15%, and subsequently aged for 20 hours at 719°C (1325°F)/AC. CMBA-6 and CMBA-8 tensile, stress-rupture and creep-rupture test samples were prepared and tested according to standard ASTM procedures. Tensile tests were performed on CMBA-6 sheet specimens which were 15% cold rolled. Average transverse tensile properties were measured at room temperature (RT), 482°C (900°F), 593°C (1100°F), 649° C (1200°F), and 704°C (1300°F). The tensile 0.2% yield strength, ultimate tensile strength and percent elongation were measured for these samples. The results are presented in Table 12 below. CMBA-6 (Heat VF 755) AVERAGE TRANSVERSE TENSILE DATA SHEET SPECIMENS; 15% COLD WORK Test Temp (°F/°C) 0.2% Yield N/mm 2 UTS N/mm 2 ELONG (%) RT 1312.8 1490.0 18.0 900/482 1199.0 1287.9 13.7 1100/593 1119.7 1245.2 14.0 1200/649 1123.2 1234.2 10.8 1300/704 1063.2 1085.9 5.6 Table 13, presented below, shows longitudinal tensile property test results for CMBA-6 specimens which were 15% cold rolled. The tensile 0.2% yield strength, ultimate tensile strength, and percent elongation were measured for the CMBA-6 samples at room temperature (RT), 482°C (900°F), 593°C (1100°F), 649°C (1200°F), and 704°C (1300°F). The 15% cold rolled CMBA-6 test results are compared with the commercially reported Waspaloy tensile properties. LONGITUDINAL TENSILE DATA COMPARISON CMBA-6 (Heat VF 755) vs. WASPALOY Test Temp (°F/°C) Alloy 0.2% Yield N/mm 2 UTS N/mm 2 ELONG (%) RA (%) RT WASPALOY 896.3 1310.0 22.0 25.0 CMBA-6 1276.2 1441.0 21.4 -- 900/482 CMBA-6 1153.5 1230.0 16.4 -- 1100/593 WASPALOY 810.1 1223.8 18.5 27.5 CMBA-6 1092.1 1179.0 15.8 -- 1200/649 WASPALOY 792.9 1206.6 15.0 30.0 CMBA-6 1065.2 1151.4 13.9 -- 1300/704 WASPALOY 775.7 1051.5 21.0 40.0 CMBA-6 1023.2 1041.1 5.7 -- Notes: · CMBA 6 -- (Heat VF 755) -- 15% Cold Worked Sheet Specimens · WASPALOY -- Forged and Fully Heat Treated to Rockwell C38 (Method "B"); Source: Engineering Alloys Digest, Inc., Upper Montclair, New Jersey. Table 14, presented below, shows results of transverse sheet specimen tensile tests undertaken with CMBA-8 materials which were cold rolled to 5% and 15% levels. Average transverse tensile properties are presented for room temperature (RT), 371°C (700°F), 482°C (900°F), 593°C (1100°F), 649°C (1200°F), 704°C (1300°F), and 760°C (1400°F) tests. CMBA-8 (Heat VF 757) AVERAGE TRANSVERSE TENSILE DATA SHEET SPECIMENS; 5%, 15% COLD WORK Test Temp (°F/°C) % Cold Work 0.2% Yield N/mm 2 UTS N/mm 2 ELONG (%) RT 5 1123.2 1505.1 25.3 15 1486.5 1725.1 7.7 700/371 5 999.1 1299.0 22.1 15 1378.3 1537.5 8.6 900/482 5 1028.7 1272.1 22.0 15 1350.0 1490.6 7.2 1100/593 5 978.4 1214.9 11.2 15 1294.8 1417.6 5.6 1200/649 5 961.1 1092.8 11.2 15 1283.1 1308.6 2.4 1300/704 5 870.1 1008.0 11.1 15 1094.9 1094.9 4.8 1400/760 5 793.6 793.6 5.8 15 686.7 686.7 2.2 Table 15, presented below, shows average longitudinal tensile property test results obtained for CMBA-8 sheet specimens, which were 5% and 15% cold rolled. CMBA-8 (Heat VF 757) AVERAGE LONGITUDINAL TENSILE DATA SHEET SPECIMENS; 5%, 15% COLD WORK Test Temp (°F/°C) % Cold Work 0.2% Yield N/mm 2 UTS N/mm 2 ELONG (%) RT 5 1095.6 1483.8 26.7 15 1492.0 1636.8 8.4 500/260 5 1001.1 1323.1 25.6 15 1446.5 1589.9 8.4 700/371 5 998.4 1276.9 25.7 15 1392.7 1520.3 8.4 900/482 5 993.5 1255.5 24.5 15 1371.4 1489.3 8.7 1100/593 5 947.3 1164.5 21.2 15 1360.3 1448.6 8.2 1200/649 5 943.2 1082.5 16.4 15 1315.5 1336.9 4.5 1300/704 5 901.8 908.7 8.3 15 1108.7 1174.2 3.1 1400/760 5 689.5 689.5 5.6 15 700.5 762.6 2.6 Elevated temperature longitudinal and transverse creep-rupture tests were also conducted with CMBA-6 and CMBA-8 sheet samples. The results for tests conducted between 649°C (1200°F) to 816°C (1500°F) are presented in Table 16 below. The tests were undertaken with CMBA-6 samples which were 15% cold rolled, while the CMBA-8 alloy was evaluated at both 5% and 15% levels. CMBA-6 (Heat VF 755) AND CMBA-8 (Heat VF 757) SHEET PRODUCT CREEP-RUPTURE DATA Test Condition Alloy Rupture Time Hours EL % Final Creep Reading Time in Hours to Reach t, Hours % Deformation 1.0% 2.0% Longitudinal Data 649°C/1061.8 N/mm 2 -8* 220.6 2.1 218.3 0.514 - - 704°C/792.8 N/mm 2 -8* 355.9 6.3 354.8 3.998 249.4 323.2 -8* 312.7 5.3 310.6 3.466 183.8 278.9 732°C/579.2 N/mm 2 -8* 512.3 6.1 511.2 4.647 268.4 421.8 -8* 623.5 10.5 623.3 9.732 146.6 407.8 732°C/620.5 N/mm 2 -8* 149.7 14.9 148.2 11.154 90.1 131.2 -6 95.2 16.0 94.9 10.054 13.3 57.0 760°C/413.7 N/mm 2 -6 438.2 4.8 437.6 2.910 184.6 337.5 -8* 1049.1 19.3 1048.8 16.766 219.4 554.7 760°C/551.6 N/mm 2 -8* 178.6 13.6 178.4 3.128 78.5 151.9 788°C/379.2 N/mm 2 -6 221.4 6.0 221.0 5.531 125.7 178.9 -8* 325.0 5.5 324.5 5.192 177.6 255.9 -8* 353.0 15.8 352.6 13.152 183.6 250.8 816°C/379.2 N/mm 2 -8* 149.7 14.9 148.2 11.154 90.1 131.2 -6 95.2 16.0 94.9 10.054 13.3 57.0 Transverse Data 732°C/517.1 N/mm 2 -6 137.6 3.1 136.4 0.730 - - 760°C/413.7 N/mm 2 -6 610.5 5.4 609.5 4.555 32.7 493.5 -8 495.4 2.7 492.0 1.868 420.2 - 788°C/310.3 N/mm 2 -6 642.8 11.0 642.5 9.363 343.1 487.9 -8 667.5 12.2 666.4 10.731 363.9 483.3 816°C/275.8 N/mm 2 -6 225.0 15.1 225.0 10.362 82.9 143.6 -8 278.0 15.0 276.8 12.056 142.0 193.2 -8* 458.9 10.9 458.2 9.366 178.2 271.7 Notes: · CMBA-6 - 15% Cold Work. · CMBA-8 - 5% Cold Work. · CMBA-8* - 15% Cold Work. A number of the creep specimens tested in this program failed when the specimens were loaded. However, it is believed that the failures were caused by unacceptably large grain sizes rather than being a consequence of alloy design. Accordingly, strict thermal cycle controls may be advantageous to providing the small grain size and grain boundary microstructures which are generally desired. Additionally, creative methods of hot working with intermediate anneal(s) prior to completion of hot working may be useful toward providing desired grain sizes. Despite the specimens which failed on loading, encouraging rupture lives and ductilities were apparent for the alloys of this invention. The test results indicated that improved alloy ductility was possible with the 5-15% cold worked materials relative to 25% cold worked CMBA-6 and CMBA-7 materials, while retaining high strength. EXAMPLE 4 23 kg (Fifty pound) samples of CMBA-6 (Heat VF790) were ESR processed into two 10.16 cm (4") diameter ingots. The ingots were homogenize-annealed using a cycle of 1163°C (2125°F) for 4 hours + 1177°C (2150°F) for 65 hours. The ingots were press forged to 5.08 cm x 5.08 cm (2" x 2") at about 1149°C (2100°F). One 5.08 cm x 5.08 cm (2" x 2") billet (Lot 1) was hot rolled to 14.275 mm (.562") diameter at about 1121°C (2050°F) and split into four sublots. One sublot (NN) was further hot rolled to 11.354 mm (.447") diameter, solution treated at 1102°C (2015°F) for 2 hours, and cold drawn to 9.906 mm (.390") diameter for a 24% reduction. A second sublot (RR) was hot rolled to .11.354 mm (.447") diameter, solution treated at 1102°C (2015°F) for 2 hours, aged at 850°C (1562°F) for 10 hours/AC, and then cold drawn to 9.906 mm (.390") diameter (24% reduction). A third sublot (MM) was hot rolled to 11.074 mm (.436") diameter, solution treated at 1102°C (2015°F) for 2 hours, aged at 800°C (1472°F) for 6 hours/AC, and then cold drawn to 9.906 mm (.390") diameter (20% reduction). The fourth sublot (PP) was hot rolled to 10.947 mm (.431") diameter, solution treated at 1102°C (2015°F) for 2 hours, aged at 850°C (1562°F) for 10 hours/AC, and then cold drawn to 9.906 mm (.390") diameter (18% reduction). All four sublots were given a final age at 732°C (1350°F) for 4 hours/AC. Threaded studs (3/8-24 x 1.5) were fabricated and tested. The results of such tests are presented in Table 17 below. The tensile tests were conducted per MIL-STD-1312, test numbers 8 and 18. Stress-rupture tests were conducted per MIL-STD-1312, test number 10. Tension-impact tests were conducted as described in Example 2 above. CMBA-6 TENSILE, STRESS-RUPTURE AND IMPACT STRENGTH DATA Property CMBA-6 (Heat VF 790, Lot 1) Sublot MM Sublot NN Sublot PP Sublot RR Tensile Strength RT UTS, N/mm 2 (ksi) 1751.3 1618.2 1656.1 1698.9 (254.0) (234.7) (240.2) (246.4) RT YS N/mm 2 (ksi) 1532.0 1432.7 1405.2 1512.7 (222.2) (207.8) (203.8) (219.4) 677°C UTS, N/mm 2 (ksi) 1468.6 1327.9 1350.7 1432.7 (213.0) (192.6) (195.9) (207.8) 677°C YS, N/mm 2 (ksi) 1278.3 1201.1 1192.1 1269.3 (185.4) (174.2) (172.9) (184.1) Stress Rupture Life, hrs. 740°C/344.7 N/mm 2 (ksi) 106 324 431 215 Tension Impact Strength, J (ft.- lbs.) Pre-exposure 169.5 290.2 189.8 180.3 (125) (214) (140) (133) Post-exposure 84.1 280.7 157.3 69.2 (62) (207) (116) (51) Notes: · Test Specimen Type: 3/8 - 24 x 1.5 studs. · All specimens solutioned for 2 hours at 1102°C (2015°F), prior to aging and cold work processing. · MM - 800°C (1475°F)/6 hrs./AC + 20% cold work + 732°C (1350°F)/4 hrs./AC. · NN - 24% cold work + 732°C (1350°F)/4 hours. · PP - 850°C (1562°F)/10 hrs./AC + 18% cold work + 732°C (1350°F)/4 hrs./AC. · RR - 850°C (1562°F)/10 hrs./AC + 24% cold work + 732°C (1350°F)/4 hrs./AC. · Results presented are averaged values. · Stress based on area at the basic pitch diameter (0.6133 cm 2 (0.09506 in. 2 )). Additional materials were evaluated which were solution treated, 24% cold worked and aged at 732°C (1350°F)/4 hours/AC (i.e., the processing method identified as NN in Table 17). Spline head bolts (3/8-24 x 1.270) and 6.4 mm (.252") diameter specimens were fabricated and tested. Tensile tests were conducted on the bolts per MIL-STD-1312, test number 8 and 18, and on the specimens per ASTM E8 and E21. Stress-rupture tests were performed on the bolts per MIL-STD-1312, test number 10. Thermal stability was evaluated by comparing the tension-impact strength and wedge tensile strength (ASTM F606) of bolts which had and had not received an elevated temperature, stressed exposure for a specific period of time. Cylindrical blanks (9.525 mm ((3/8") diameter x 2.54 cm (1") long) were machined from the drawn and aged bar, and double shear tested per MIL-STD-1312, test number 13. These test results are presented in Table 18 below. CMBA-6 TENSILE, STRESS-RUPTURE, IMPACT AND WEDGE TENSILE STRENGTH DATA Property CMBA-6 Alloy (Heat VF 790, Lot 1) A. BOLTS RT Tensile UTS, N/mm 2 1609.9 YS, N/mm 2 1436.2 677°C Tensile UTS, N/mm 2 1289.3 YS, N/mm 2 1153.5 704°C Tensile UTS, N/mm 2 1275.5 YS, N/mm 2 1142.5 704°C/689.5 N/mm 2 Stress-Rupture Life, hours 151.9 Tension Impact Strength, J (ft.-lbs.) Pre-exposure 329.5 Post-exposure #1 203.4 Post-exposure #2 164.1 Tensile Strength, N/mm 2 1609.9 Pre-exposure 1536.8 Post-exposure #2 2° Wedge Tensile Strength, N/mm 2 1615.4 Pre-exposure 1505.1 Post-exposure #1 4° Wedge Tensile Strength, N/mm 2 1587.9 Pre-exposure 1474.8 Post-exposure #1 B. SPECIMENS RT Tensile UTS, N/mm 2 1585.8 0.2% YS, N/mm 2 1406.5 Elong., % 17 RA, % 40 Shear Stress, N/mm 2 974.2 Notes: · Test Articles: 3/8-24 x 1.270 spline head bolts, 6.35 mm (.252") diameter specimens and 9.525 mm (3/8") diameter x 2.54 cm (1") pins. · Condition: Solutioned + 24% cold work + 732°C (1350°F)/4 hours/AC. · Results presented are averaged values. · Stress for bolts based on area at the basic pitch diameter (0.6133 cm 2 (0.09506 in. 2 )). · Exposure cycle #1: 704°C/344.7 N/mm 2 (1300°F/50 ksi)/100 hours. · Exposure cycle #2: 566°C/951.5 N/mm 2 (1050°F/138 ksi)/640 hours. Creep tests were conducted per ASTM E139 on 6.35 mm (.252") diameter specimens. The times to 0.1% and 0.2% creep were measured. These test results are presented in Table 19 below. CMBA-6 (Heat VF 790, Lot 1) CREEP-RUPTURE DATA Test Conditions Time to 0.1% Creep, hrs. Time to 0.2% Creep, hrs. 649°C/620.5 N/mm 2 547.3 2192.3 649°C/517.1 N/mm 2 459.1 1916.3 649°C/448.2 N/mm 2 412.7 4285.6 704°C/344.7 N/mm 2 185.3 995.4 704°C/241.3 N/mm 2 611.5 4284.5 Notes: · Test Article: 6.35 mm (.252") diameter specimens. · Condition: Solutioned + 24% cold work + 732°C (1350°F)/4 hours/AC. The thermal expansion coefficient of CMBA-6 alloy was measured on 9.525 mm (.375") diameter x 5.08 cm (2") long specimens per ASTM E228. The test results are presented in Table 20 below. CMBA-6 (Heat VF 790, Lot 1) THERMAL EXPANSION COEFFICIENT DATA Temperature Range a(m/m/°C x 10 -6 ) 20°C - 425°C 13.5 20°C - 540°C 13.9 20°C - 650°C 14.4 20°C - 705°C 14.8 Notes: · Test Article: 9.525 mm (0.375") diameter x 5.08 cm (2.0") long pins. · Condition: Solutioned + 24% cold work + 732°C (1350°F)/4 hours/AC. Three separate stress-relaxation trials were conducted on bolts using the cylinder method described in MIL-STD-1312, test number 17. A review of the hardware utilized and the test results are presented in Table 21 below. CMBA-6 (Heat VF 790, Lot 1) STRESS-RELAXATION DATA Original Stress N/mm 2 Exposure Relaxation % Relaxed Remaining Stress N/mm 2 Temp. °C Time hrs. joint, N/mm 2 bolt, N/mm 2 a. Cylinder Material = MP210 Alloy Nut Material = SPS FN1418 (Waspaloy Silver plated, lock tapped out) 1312.1 704 500 114.5 1115.6 85.0 82.0 1201.1 704 500 102.0 1019.7 84.8 79.3 502.6 704 500 114.5 299.9 59.7 88.3 b. Cylinder Material = MP210 Alloy Nut Material = SPS FN1418 (Waspaloy Silver plated, lock tapped out) 951.5 566 640 63.4 326.1 34.3 561.9 c. Cylinder Material = MP210 Alloy Nut Material = GE J627P06B (Waspaloy unplated lock in) 586.1 704 300 198.6 153.1 60.0 234.3 Notes: · Test Article: 3/8-24 spline-head bolts (threads rolled after aging). · Specimens solutioned + 24% cold worked + aged at 732°C (1350°F)/4 hrs./AC. The second 5.08 cm x 5.08 cm (2" x 2") billet from Heat VF790 (Lot 2) was hot rolled at about 1121°C (2050°F) to 11.354 mm (.447") diameter, solution treated at 1102°C (2015°F) for 2 hours, cold drawn 24% to 9.906 mm (.390") diameter, and aged at 732°C (1350°F) for 4 hours. Standard 6.4 mm (.252") diameter specimens, notched specimens (notch tip radius machined to achieve K T of 3.5 and 6.0), and spline head bolts (3/8-24 x 1.270) were fabricated and tested. Density was determined to be 8.62 kg/m 3 (.311 lb./in. 3 ) by measuring the weight and volume of a cylindrical sample. Tensile tests were conducted on the smooth and notched specimens per ASTM E8 and E21; the results are presented below in Tables 22 and 23, respectively. CMBA-6 (Heat VF 790, Lot 2) SMOOTH TENSILE DATA Test Temperature, °C UTS, N/mm 2 0.2% YS, N/mm 2 E % RA % RT 1583.0 1455.5 16.7 38.0 427 1382.4 1243.8 15.0 39.7 538 1336.9 1233.5 14.7 41.5 593 1306.6 1202.4 14.7 40.3 649 1289.3 1164.5 14.0 42.9 704 1298.6 1130.1 10.0 43.1 760 1152.1 1054.9 7.7 16.0 Notes: · Results presented are averaged values. · Test Article: 6.4 mm (.252") diameter specimens. · Condition: Solutioned + 24% cold work + 732°C (1350°F)/4 hours/AC. CMBA-6 (Heat VF 790, Lot 2) NOTCHED TENSILE DATA Test Temperature K T NTS, N/mm 2 NTS/UTS RT 3.5 2413.2 1.52 RT 6.0 2399.4 1.51 649°C 6.0 1985.3 1.53 704°C 6.0 1758.2 1.41 Notes: · Results presented are averaged values. · Test Article: D = 6.4 mm (.252") diameter; d = 4.496 mm (.177") diameter; r = variable to achieve given K T . · Condition: Solutioned + 24% cold work + 732°C (1350°F)/4 hours/AC. Tensile tests were performed on the bolts per MIL-STD-1312, test numbers 8 and 18. These test results are presented in Table 24 below. CMBA-6 (Heat VF 790, Lot 2) BOLT TENSILE DATA Test Temperature, °C UTS, N/mm 2 YS, N/mm 2 RT 223 1337.6 200 213 1289.3 400 206 1241.1 600 203 1254.8 800 192 1199.7 1000 189 1192.8 1100 188 1172.1 1200 185 1165.2 1200 (2° wedge) 183 1117.0 1300 182 1158.3 1400 170 1068.7 Notes: · Test Article: 3/8-24 x 1.270 spline head bolts. · Condition: Solutioned + 24% cold work + 732°C (1350°F)/4 hours/AC. · Results presented are averaged values. · Stress based on area at the basic pitch diameter (0.6133 cm 2 ) ((0.09506 in. 2 )). Fatigue tests were run on the bolts per MIL-STD-1312, test number 11. The tests were conducted at room temperature (RT) with an R-ratio of 0.1 or 0.8, at 260°C (500°F) with an R-ratio of 0.6, and at 704°C (1300°F) with an R-ratio of 0.05. These test results are presented in Table 25 below. Stress-rupture tests were performed on the bolts per MIL-STD-1312, test number 10. These test results are presented in Table 26 below. CMBA-6 (Heat VF 790, Lot 2) BOLT STRESS-RUPTURE DATA Test Conditions Time to Failure, hours 593°C/1206.6 N/mm 2 36.5 649°C/1034.2 N/mm 2 28.5 649°C/1034.2 N/mm 2 103.2 677°C/772.2 N/mm 2 189.6 704°C/689.3 N/mm 2 160.3 704°C/689.3 N/mm 2 2.5 704°C/689.3 N/mm 2 147.1 760°C/413.7 N/mm 2 Notes: · Test Article: 3/8-24 x 1.270 spline head bolts. · Condition: Solutioned + 24% cold work + 732°C (1350°F)/4 hrs./AC. · Results presented are averaged values. · Stress based on area at the basic pitch diameter ((0.6133 cm 2 (0.09 506 in 2 )). Thermal stability was evaluated using 1) bolts exposed to constant stress and temperature for 100 hours and 2) stress relaxation tested bolts, and comparing their subsequent tension-impact strength, 2° wedge tensile strength, and 4° wedge tensile strength to that of unexposed bolts. These test results are presented in Table 27 and Table 28 below. CMBA-6 (Heat VF 790, Lot 2) BOLT THERMAL STABILITY - SUSTAINED LOAD EXPOSURE Bolt History Room Temperature Test Results Initial Stress N/mm 2 Final Stress N/mm 2 Temperature °C Time Hours 2° Wedge Tensile Strength N/mm 2 Tension-Impact Strength J(ft.lbs) No Exposure 1569.9 322.7 1560.3 315.9 Sustained Load Exposure 861.8 861.8 593 100 1570.6 183.1 1566.5 183.1 517.1 517.1 649 100 1573.4 172.2 1562.4 168.1 6430.9 430.9 677 100 1563.0 187.1 1561.7 155.9 344.7 344.7 704 100 1503.7 184.4 1488.6 173.6 Notes: · Test Article: 3/8-24 x 1.270 spline head bolts. · Condition: Solutioned + 24% cold work + 732°C (1350°F)/4 hrs./AC. · Stress based on area at the basic pitch diameter ((0.6133 cm 2 (0.09 506 in 2 )). CMBA-6 (Heat VF 790, Lot 2) BOLT THERMAL STABILITY - STRESS-RELAXATION EXPOSURE Bolt History Room Tempereture Test Results Initial Stress N/mm 2 Final Stress N/mm 2 Temperature °C Time Hours 2° Wedge Tensile Strength N/mm 2 4° Wedge Tensile Strength N/mm 2 Tension-Impact Strength J ft.lbs) No Exposure 1569.9 322.7 1560.3 315.9 Stress-Relaxation Exposure 862.5 581.9 649 100 210.1 681.9 541.2 100 1381.7 801.9 521.2 649 500 154.6 721.9 501.2 500 1524.4 801.9 481.3 649 1000 164.1 721.9 461.3 1000 1293.5 581.2 343.9 704 100 195.3 541.2 361.3 100 1499.6 581.9 260.6 704 250 151.9 561.2 260.6 704 500 1444.5 1287.9 581.2 260.6 500 561.2 200.6 500 24.9 951.5 561.9 566 640 64.1 1312.1 196.5 704 500 1410.0 1201.1 181.3 500 1389.3 502.6 202.7 500 23.4 Notes: · Test Article: 3/8-24 x 1.270 spline head bolts. · Condition: Solutioned + 24% cold work + 732°C (1350°F)/4 hrs./AC. · Stress based on area at the basic pitch diameter ((0.6133 cm 2 (0.09 506 in 2 )). Another stress-relaxation trial was conducted on bolts using the cylinder method described in MIL-STD-1312, test number 17. A review of the hardware utilized and the test results are presented in Table 29 below. CMBA-6 (Heat VF 790, Lot 2) STRESS-RELAXATION DATA Original Stress N/mm 2 Exposure Relaxation % Relaxed Remaining Stress N/mm 2 Temp. °C Time hrs. joint, N/mm 2 bolt, N/mm 2 Cylinder Material = Waspaloy Nut Material = SPS FN1418 (Waspaloy Silver plated, lock tapped out) 862.5 649 100 120.7 160.0 32.6 581.9 681.9 649 100 80.0 60.0 20.6 541.9 801.9 649 500 120.7 160.6 35.0 520.6 721.9 649 500 140.7 80.0 30.6 501.2 801.9 649 1000 120.7 200.6 40.0 480.6 741.9 649 1000 100.0 180.0 37.8 461.9 581.2 704 100 180.6 60.0 41.4 340.6 541.2 704 100 180.6 0 33.3 360.6 581.9 704 250 220.6 100.0 55.2 261.3 561.2 704 500 200.6 100.0 53.6 260.6 581.2 704 500 240.6 120.7 62.1 219.9 561.2 704 500 300.6 60.0 64.3 200.6 Notes: · Test Article: 3/8-24 spline-head bolts (threads rolled after aging). · Specimens solutioned + 24% cold worked + aged at 732°C (1350°F)/4 hrs./AC. EXAMPLE 5 A 682 kg (1500 pound) heat (VV 584) of CMBA-6 was VIM-processed to 24.13 ccm (9½") diameter, ESR-processed to 36.83 cm (14½") diameter, homogenize-annealed at 1163°C (2125°F)/4 hours + 1177°C (2150°F)/65 hours, and hot forged at about 1121°C (2050°F) to 11.43 cm (4¼") diameter. Some of the material was divided into seven lots and processed to 10.033 mm (.395") diameter bar as described below in Table 30: CMBA-6 (Heat VV 584) PROCESSING CONDITIONS Lot # Hot Rolled at 1121°C to: Solution Treat Cycle Cold Draw Percent 1 11.506 mm 1074°C/1 hr 24 2 11.836 mm 1074°C/1 hr 28 3 12.167 mm 1074°C/1 hr 32 4 11.506 mm 1093°C/2 hrs 24 5 11.836 mm 1093°C/2 hrs 28 6 12.167 mm 1093°C/2 hrs 32 7 11.506 mm 1093°C/2 hrs 24 Notes: · Lots 1 through 6 drawn in 3 passes. · Lot 7 drawn in 1 pass. All seven sublots were given a final age at 732°C (1350°F) for 4 hours/AC. Standard 6.4 mm (.252") diameter specimens were fabricated from each sublot and tensile tested per ASTM E8 and E21. Table 31, presented below, shows the results of the tensile tests undertaken with CMBA-6 material, which was processed as described above in Table 30, and tested at room temperature (RT), 427°C (800°F), 538°C (1000°F), 649°C (1200°F) and 760°C (1400°F). CMBA-6 (HEAT VV 584) SMOOTH TENSILE PROPERTIES Test Lot No. Temp, °F 1 2 3 4 5 6 7 RT UTS N/mm 2 1914.0 1933.3 2061.5 234.0 1654.7 1760.9 1651.3 0.2% YS 1845.7 1887.1 2022.1 215.8 1555.5 1649.5 1547.9 Elong. % 9.0 8.0 6.0 9.0 10.0 8.0 8.0 RA % 30.9 30.0 27.6 34.2 34.5 32.3 31.9 427 UTS N/mm 2 1679.6 1739.5 1814.0 211.1 1447.9 1753.2 1436.2 0.2% YS 1617.5 1710.6 1752.0 203.0 1764.5 1503.1 1347.9 Elong. % 10.0 8.0 5.5 8.5 10.0 8.0 11.0 RA % 31.8 27.6 26.5 33.5 34.5 32.5 33.2 538 UTS N/mm 2 1635.4 1723.7 1767.1 201.8 1408.6 1481.0 1388.6 0.2% YS 1570.6 1695.4 1736.8 193.2 1331.4 1420.3 1316.9 Elong. % 10.0 8.0 5.0 9.0 10.0 8.0 11.0 RA % 31.6 27.9 25.2 34.2 33.8 35.8 35.1 649 UTS, N/mm 2 1598.9 1761.6 1719.6 196.3 1376.9 1437.6 1357.6 0.2% YS 1508.6 1727.8 1643.0 184.0 1285.9 1368.6 1248.6 Elong. % 10.0 5.5 5.0 8.0 10.0 8.0 10.5 RA % 34.4 13.0 22.4 33.5 31.2 33.1 33.5 760 UTS, N/mm 2 1541.2 1521.0 1634.1 183.1 1334.8 1148.3 1301.0 0.2% YS 1420.3 1399.6 1518.9 174.6 1259.7 1141.2 1248.6 Elong. % 9.5 6.0 8.0 8.0 10.0 - 6.0 RA % 20.3 13.0 41.4 33.2 30.8 - 31.2 Note: · Results presented are averaged values. · Test Article: 6.4 mm (.252") diameter specimen · Condition: see Table 30 + 732°C ((1350°F)/4 hours/AC In addition to the 10.033 mm (.395") diameter bar described above, Heat VV 584 was used to make 13.589 mm (.535") and 19.558 mm (.770") diameter bars. They were produced by rolling the hot forged stock at about 1121°C (2050°F) to about 15.596 mm (.614") and 22.428 mm (.883") diameters, respectively, solution treating at 1093°C (2000°F)/2 hours/AC, and cold drawing 24% to the desired 13.589 mm (.535") and 19.558 mm (.770") dimensions. The bars were given a final age at 732°C (1350°F) for 4 hours/AC. Various tests were conducted utilizing these materials as described below. Double shear tests were performed on cylindrical blanks per MIL-STD-1312, test number 13. These test results are presented in Table 32 below. CMBA-6 (Heat VV 584) DOUBLE SHEAR STRENGTH DATA Test Diameter, mm. N/mm 2 9.525 (Lot 4) 1017.7 1017.7 12.7 972.9 963.9 19.05 1014.2 1006.6 Thermal conductivity measurements were performed on a right cylinder specimen, 2.54 cm (1.000") diameter by 2.54 cm (1.000") long per ASTM E1225. There were three thermocouple holes in the specimen, and the test temperature ranged from -- 196°C (320°F) to 704°C (1300°F). The test results are presented in Table 33 below. CMBA-6 (Heat VV 584) THERMAL CONDUCTIVITY DATA Temperature °C Thermal Conductivity w/m·K -186 8.75 -106 9.20 -18 10.05 105 11.29 195 12.59 296 13.86 397 15.32 493 17.48 591 19.08 690 20.70 Electrical resistivity measurements were performed using the Form Point Probe Method on a 7.62 cm (3.00") long by 6.35 mm (0.250") square specimen per ASTM B193. The test temperature ranged from -196°C (-320°F) to 704°C (1300°F). The test results are presented in Table 34 below. CMBA-6 (Heat VV 584) ELECTRICAL RESISTIVITY DATA Temperature °C Electrical Resistivity ohm-cm x 10 6 -186 112.32 -163 112.67 -141 113.39 -123 114.07 -55 115.49 -22 116.89 23 117.55 92 118.24 203 120.37 313 122.35 428 126.34 543 129.18 650 131.24 702 133.96 Specific heat measurements were performed using the Bunsen Ice Calorimeter Technique on a 3.81 cm (1.5") long by 6.35 mm (0.25") inch square specimen per ASTM D2766. The test temperature ranged from 21°C (70°F) to 704°C (1300°F). The test results are presented in Table 35 below. CMBA-6 (Heat VV 584) ENTHALPY/SPECIFIC HEAT DATA Temperature °C Enthalpy, J/kg Temperature °C Specific Heat J/kg·K 0 0 0 414 50 43710 50 435 155 134915 100 452 278 114107 150 469 397 350067 200 486 558 498543 250 498 706 638487 300 511 350 519 450 523 500 523 550 528 600 532 700 544 Young's modulus, shear modulus and Poisson's ratio were determined by performing dynamic modulus measurements on a 12.7 mm (0.500") diameter by 5.08 cm (2.000") long specimen per ASTM E494. The test temperature ranged from 21°C (70°F) to 704°C (1300°F). The results are presented in Table 36 below. CMBA-6 (Heat VV 584) DYNAMIC MODULUS DATA Temperature °C V l km/s V t km/s Elastic Modulus kN/mm 2 Shear Modulus kN/mm 2 Poisson's Ratio 22 5.73 3.13 216 83.8 0.287 225 5.64 3.05 206 79.6 0.293 323 5.57 2.93 192 73.4 0.309 478 5.47 2.88 185 70.9 0.309 544 5.32 2.80 175 67.0 0.308 737 5.19 2.58 152 56.9 0.336 While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of this invention will be obvious to those skilled in the art. The appended claims and this invention generally should be construed to cover all such obvious forms and modifications which are within the scope of the present invention.

Claims: A high-strength nickel-cobalt based alloy having a high thermal stability and microstructural stability at elevated temperatures up to about 760°C comprising the following elements in percent by weight: Carbon 0.005-0.03 Boron 0.01-0.02 Niobium 0.9-1.3 Chromium 13.0-17.5 Molybdenum 2.7-4.0 Cobalt 24.5-34.0 Aluminum 0.9-1.1 Titanium 1.9-4.0 Tantalum 3.8-5.0 Tungsten 1.8-3.0 Vanadium 0-0.01 Zirconium 0-0.02 Silicon 0-0.025 Manganese 0-0.01 Iron 0-0.1 Copper 0-0.01 Phosphorus 0-0.01 Sulfur 0-0.002 Nitrogen 0-0.001 Oxygen 0-0.001 Nickel + Incidental Impurities Balance said alloy having a phasial stability number N v3B less than 2.50. The alloy of claim 1, wherein said alloy has a platelet phase and a gamma prime phase dispersed in a face-centered cubic matrix, and said alloy further being substantially free of embrittling phases. The alloy of claim 1, wherein said alloy has been cold worked to achieve a reduction in cross-section of from 10% to 40%. The alloy of claim 1, wherein said alloy has an increased resistance to creep under high stress, high temperature conditions up to about 816°C (1500°F). The alloy of claim 1, wherein sad alloy has the capability of withstanding 200N/mm 2 (29 ksi) at 704°C (1300°F) for 1000 hours before exhibiting 0.1% creep deformation. The alloy of claim 1, wherein said alloy has been aged at a temperature of from about 427°C (800°F) to about 760°C (1400°F) for about 1 hour to about 50 hours after cold working. The alloy of claim 1, wherein said alloy has been aged at a temperature of from about 649°C (1200°F) to about 899°C (1650°F) for about 1 hour to about 200 hours, cold worked to achieve a reduction in cross-section of 10% to 40%, and then aged again at a temperature of from about 427°C (800°F) to about 7600C (1400°F) for about 1 hour to about 50 hours. An article made from the alloy of claim 1. The article of claim 8, wherein said article is a fastener. A high-strength fastener made from an alloy having a high thermal stability and microstructural stability at elevated temperatures up to about 760°C, comprising the following elements in percent by weight: Carbon 0.005-0.03 Boron 0.01-0.02 Niobium 0.9-1.3 Chromium 13.0-17.5 Molybdenum 2.7-4.0 Cobalt 24.5-34.0 Aluminum 0.9-1.1 Titanium 1.9-4.0 Tantalum 3.8-5.0 Tungsten 1.8-3.0 Vanadium 0-0.01 Zirconium 0-0.02 Silicon 0-0.025 Manganese 0-0.01 Iron 0-0.1 Copper 0-0.01 Phosphorus 0-0.01 Sulfur 0-0.002 Nitrogen 0-0.001 Oxygen 0-0.001 Nickel + Incidental Impurities Balance said alloy having a phasial stability number N v3B less than 2.50. The fastener of claim 10, wherein said alloy has a platelet phase and a gamma prime phase dispersed in a face-centered cubic matrix, and said alloy further being substantially free of embrittling phases. The fastener of claim 10, wherein said alloy has been cold worked to achieve a reduction in cross-section of from 10% to 40%. The fastener of claim 10, wherein said alloy has an increased resistance to creep under high stress, high temperature conditions up to about 816°C (1500°F). The fastener of claim 10, wherein said fastener has a stress-rupture life at 704°C (1300°F)/689.5 N/mm 2 (100ksi) condition greater than 150 hours. The fastener of claim 10, wherein said alloy has been aged at a temperature of from about 427°C (800°F) to about 760°C (1400°F) for about 1 hour to about 50 hours after cold working. The fastener of claim 10, wherein said alloy has been aged at a temperature of from about 649°C (1200°F) to about 899°C (1650°F) for about 1 hour to about 200 hours, cold worked to achieve a reduction in cross-section of 10% to 40%, and then aged again at a temperature of from about 427°C (800°F) to about 760°C (1400°F) for about 1 hour to about 50 hours. The fastener of claim 10, wherein said fastener is a bolt, screw, nut, rivet, pin, or collar.

Inventors: ERICKSON GARY L, ERICKSON, GARY L.
Applicants: SPS TECHNOLOGIES, SPS TECHNOLOGIES, INC.
Application year: 1993
Main classification: C22C19
IPC codes: C22F1, C22C19, C22C30