Title of Invention	"HOT CORROSION SINGLE CRYSTAL NICKEL-BASED SUPERALLOYS"
Abstract	A process for manufacturing a hot corrosion resistant nickel-based superalloy composition comprising mixing and melting the following elements in percent by weight: Chromium about 11.5-13.5 Cobalt about 5.5-8.5 Molybdenum about 0.40-0.55 Tungsten about 4.5-5.5 Tantalum about 4.5-5.8 Columbium about 0.-05-0.25 Aluminum about 3.4-3.8 Titanium about 4.0-4.4 Hafnium about 0.01 -0.06 Nickel + Incidental balance Impurities Carbon about 0.0-0.05 Boron about 0-0.03 Zirconium about 0.0.03 Rhenium about 0-0.25 Silicon about 0-0.10 Manganese about 0.0.10 And cooling to obtain said superalloy composition having a phasial stability number NV3B 'ess than about 2.45.

Title of Invention

"HOT CORROSION SINGLE CRYSTAL NICKEL-BASED SUPERALLOYS"

Abstract

A process for manufacturing a hot corrosion resistant nickel-based superalloy composition comprising mixing and melting the following elements in percent by weight: Chromium about 11.5-13.5 Cobalt about 5.5-8.5 Molybdenum about 0.40-0.55 Tungsten about 4.5-5.5 Tantalum about 4.5-5.8 Columbium about 0.-05-0.25 Aluminum about 3.4-3.8 Titanium about 4.0-4.4 Hafnium about 0.01 -0.06 Nickel + Incidental balance Impurities Carbon about 0.0-0.05 Boron about 0-0.03 Zirconium about 0.0.03 Rhenium about 0-0.25 Silicon about 0-0.10 Manganese about 0.0.10 And cooling to obtain said superalloy composition having a phasial stability number NV3B 'ess than about 2.45.

Full Text	1. Field of the Invention This invention relates to single crystal nickel-based superalloys and, more particularly, single crystal nickel-based superalloys and articles made therefrom having increased resistance to bare hot corrosion for use in gas turbine engines. 2. Description of the Prior Art Advances over recent years in the metal temperature and stress capability of single crystal articles have been the result of the continuing development of single crystal superalloys, as well as improvements in casting processes and engine application technology. These single crystal superalloy articles include rotating and stationary turbine blades and vanes found in the hot sections of gas turbine engines. Gas turbine engine design goals have remained the same during the past decades. These goals include the desire to increase engine operating temperature, rotational speed, fuel efficiency, and engine component durability and reliability. Prior art attempts to provide alloys to help achieve these design goals for industrial gas turbine engine applications include U.S. Patent No. 4,677,035, Fiedler et al., which discloses a nickel-base single crystal alloy composition consisting essentially of, in percent by weight, 8.0-14.0% c romium, 1.5-6.0% cobalt, 0.5-2.0% molybdenum, 3.0-10.0% u^..g~ten, 2.5-7.0% titanium, 2.5-7.0% aluminum, 3.0-6.0% tan Mm, and the balance nickel. However, the alloy compositions taught by this reference, while possessing relatively high strength at prolonged or repeated exposure to high temperatures, are susceptible to the accelerated corrosive effect of the hot gas environment in which components fabricated from the alloys are exposed to when used in gas turbines. Also, U.K. Patent Application Publication No. 2153848A discloses nickel-base alloys having a composition within the range of 13-15.6% chromium, 5-15% cobalt, 2.5-5% molybdenum, 3-6% tungsten, 4-6% titanium, 2-4% aluminum, and the balance essentially nickel without intentional additions of carbon, boron or zirconium, which are fabricated into single crystals. Although the alloys taught by this reference claim an improvement in hot corrosion resistance accompanied by an increase in creep rupture properties, the need remains in the art for single crystal superalloys for industrial gas turbine applications having a superior combination of increased hot corrosion resistance, oxidation resistance, mechanical strength, large component castability and adequate heat treatment response. Single crystal articles are gemarally produced having the low-modulus (001) crystallographic orientation parallel to the component dendritic growth pattern or blade stacking axis. Face-centered cubic (FCC) superalloy single crystals grown in the (001) direction provide extremely good thermal fatigue resistance relative to conventionally cast polycrystalline articles. Since these single crystal articles have no grain boundaries, alloy design without grain boundary strengtheners, such as carbon, boron aind zirconium, is possible. As these elements are alloy melting point depressants, their essential elimination from the alloy design provides a greater potential for high temperature mechanical strength achievement since more complete gamma prime solution and microstructural homogenization can be achieved relative to directionally solidified (DS) columnar grain and conventionally cast materials, made possible by a higher incipient melting temperature. These process benefits are not necessarily realized unless a multi-faceted alloy design approach is undertaken. Alloys must be designed to avoid tendency for casting defect formation such as freckles, slivers, spurious grains and recrystalllzation, particularly when utilized for large cast components. Additionally, the alloys must provide an adequate heat treatment "window" (numeric difference between an alloy's gamma prime solvus and incipient melting point) to allow for nearly complete gamma prime solutioning. At the same time, the alloy compositional balance should be designed o ~, ..vide an adequate blend of engineering properties necr-sar • for operation in gas turbine engines. Selected properties jer orally considered important by gas turbine engine designers incl 'da: elevated temperature creep-rupture strength, thermo-mechanical fatigue resistance, impact resistance, hot corrosion and oxidation resistance, plus coating performance. In particular, industrial turbine designers require unique blends of hot corrosion and oxidation resistance, plus good long-term mechanical properties. An alloy designer can attempt to improve one or two of these design properties by adjusting the compositional balance of known superalloys. However, it is extremely difficult to improve more than one or two of the design properties without significantly or even severely compromising some of the remaining properties. The unique superalloy of the present invention provides an excellent blend of the properties necessary for use in producing single crystal articles for operation in industrial and marine gas turbine engine hot sections. SUMMARY OF THE INVENTION This invention relates to a hot corrosion resistant nickel-based superalloy comprising the following elements in percent by weight: from about 11.5 to about 13.5 percent chromium, from about 5.5 to about 8.5 percent cobalt, from about 0.40 to about 0.55 perosnt molybdenum, from about 4.5 to about 5 percent tungsten, froifr about 4.5 ^to about 5.8 percent -antalum, from about 0.^5 co about 0.25 percent columbium, from about 3.4 to about 3.8 percent aluminum, from about 4.0 to about 4.4 percent titanium, from about 0.01 to about 0.06 percent hafnium, and the balance nickel plus incidental impurities, the superalloy having a phasial stability number N^g less than about 2.45. Advantageously, the sum of aluminum plus titanium in this superalloy composition is from 7.4 to 8.2 percent by weight. Also, it is advantageous to have a Ti:Al ratio greater than 1 and a Ta:W ratio greater than 1 in the composition of the present invention. Although incidental impurities should be kept to the least amount possible, the superalloy can also be comprised of from about 0 to about 0.05 percent carbon, from about 0 to about 0.03 percent boron, from about 0 to about 0.03 percent zirconium, from about 0 to about 0.25 percent rhenium, from about 0 to about 0.10 percent silicon, and from about 0 to about 0.10 percent manganese. In all cases, the base element is nickel. This invention provides a single crystal superalloy having an increased resistance to hot corrosion, an increased resistance to oxidation, and increased creep-rupture strength. Single crystal articles can be suitably made from the superalloy of this invention. The article can be a component for a gas turbine engine and, more particularly, the component can be a gas turbine blade or gas turbine vane. The superalloy compositions of this invention have a critically balanced alloy chemistry which results in a unique blend of desirable properties, including an increased resistance to hot corrosion, which are particularly suitable for industrial and marine gas turbine applications. These properties include: excellent bare hot corrosion resistance and creep-rupture strength; good bare oxidation resistance; good single crystal component castability, particularly for large blade and vane components; good solution heat treatment response; adequate resistance to cast component recrystallization; adequate component coatability and microstructural stability, such as long-term resistance to the formation of undesirable, brittle phases called topologically close-packed (TCP) phases. Accordingly, it is an object of the present to provide superalloy compositions and single crystal articles made therefrom having a unique blend of desirable properties, including increased hot corrosion resistance. It is a further object of the present invention to provide superalloys and single crystal articles made therefrom for use in industrial and marine gas turbine engines. These and other objects and advantages of the present invention will be apparent to those skilled in the art upon reference to the following description of the preferred -8- embodiments . According to the- present invention relates to a process for manufacturing a hot corrosion resistant nickel -based superalloy composition comprising mixing and melting the following elements in percent by weight: Chromium about 11.5-13.5 Cobalt about 5.5-8.5 Molybdenum about 0.40-0.55 Tungsten about 4.5-5.5 Tantalum about 4.5-5.8 Columbium about 0.05-0.25 Aluminum about 3.4-3.8 Titanium about 4.0-4.4 Hafnium about 0.01-0.06 Nickel + Incidental balance Impurities Carbon about 0-0.05 Boron about 0-0.03 Zirconium about 0-0.03 Rhenium about 0-0.25 Silicon about 0-0.10 Manganese about 0-0.10 and cooling to obtain said superalloy composition having a phasial stability number N- less than about 2.45. The composition resulting from the process is not a mere admixture but a synergistic composition where all the components are not reacting but are interacting with each other to show unexpected properties. embodiments. BRIEF DESCRIPTION OF THE/DRAWINGS V FIG. 1 is a chart of hot corrosion test results performed at three exposure temperatures on one embodiment of this invention and on four other alloys. FIG. 2 is a graphical comparison of hot corrosion data from tests performed at 732°C (1350°F) on one embodiment of this invention and on two other alloys. FIG. 3 is a graphical comparison of hot corrosion data from tests performed at 899°C (1650°F) on one embodiment of this invention and on two other alloys. FIG. 4 is a graphical comparison of alloy strength and hot corrosion data from tests performed on one embodiment of this invention and on six other alloys. FIG. 5 is a graphical comparison of oxidation data from tests performed at 1000°C (1832°F) on one embodiment of this invention and on two other alloys. FIG. 6 is a graphical comparison of oxidation data from tests performed at 1010°C (1850°F) on one embodiment of the present invention and on two other alloys. FIG. 7 is a graphical comparison of alloy strength and oxidation data from tests performed on one embodiment of this invention and on six other alloys. DESCRIPTION OF THE PREFERRED EMBODIMENTS The hot corrosion resistant nickel-based superalloy of the present invention comprises the following elements in percent by weight: 'Chromium Cobalt Molybdenum Tungsten Tantalum Columbium Aluminum Titanium Hafnium Nickel + Incidental Impurities about 11.5-13.5 about 5.5-8.5 about 0.40-0.55 about 4.5-5.5 about 4.5-5.8 about 0.05-0.25 about 3.4-3.8 about 4.0-4.4 about 0.01-0.06 balance This superalloy composition also has a phasial stability number less than about 2.45. Further, this invention has a critically balanced alloy chemistry which results in a unique blend of desirable properties useful for industrial and marine gas turbine engine applications. These properties include a superior blend of bare hot corrosion resistance and creep-rupture strength relative to prior art single crystal superalloys for industrial and marine gas turbine applications, bare oxidation resistance, single crystal component castability, and microstructural stability, including resistance to TCP phase formation under high stress, high temperature conditions. Superalloy chromium content is a primary contributor toward attaining superalloy hot corrosion resistance. The supsralioys of the present invention have a relatively high chromium content since alloy hot corrosion resistance was one of the primary design criteria in the development of these alloys. The chromium is about 11.5-13.5% by weight. Advantageously, the chromium content is from 12.0% to 13.0% by weight. Although chromium provides hot corrosion resistance, it may also assist with the alloys' oxidation capability. Additionally, this superalloys' tantalum and titanium contents, as well as its Ti:Al ratio being greater than 1, are beneficial for hot corrosion resistance attainment. However, besides lowering the alloys' gamma prime solvus, chromium contributes to the formation of Cr and W-rich TCP phase and must be balanced accordingly in these compositions. In one embodiment of the present invention, the cobalt content is about 5.5-8.5% by weight. In another embodiment of the present invention, the cobalt content is from 6.2% to 6.8% by weight. The chromium and cobalt levels in these superalloys assist in making the superalloy solution heat treatable, since both elements tend to decrease an alloy's gamma prime solvus. Proper balancing of these elements in the present invention in tandem with those which tend to increase the alloy's incipient melting temperature, such as tungsten and tantalum, result in superalloy compositions which have desirable solution heat treatment windows (numerical difference between an alloy's incipient melting point and its gamma prime solvus), thereby facilitating full gamma prime solutioning. The cobalt content is also beneficial to the superalloy's solid solubility. The tungsten content is about 4.5-5.5% by weight and, advantageously, the amount of tungsten is from 4.7% to 5.3% by weight, Tungsten is added in these compositions since it is an effective solid solution strengthener and it can contribute to strengthening the gamma prime. Additionally, tungsten is effective in raising the alloy's incipient melting temperature. Similar to tungsten, tantalum is a significant solid solution strengthener in these compositions, while also contributing to enhanced gamma prime particle strength and volume fraction. The tantalum content is about 4.5-5.8% by weight and, advantageously,, the tantalum content is from 4.9% to 5.5% by weight. In these compositions, tantalum is beneficial since it helps to provide bare hot corrosion and oxidation resistance, along with aluminide coating durability. Additionally, tantalum is an extractive single crystal alloy additive in these compositions since it assists in preventing "freckle" defect formation during the single crystal casting process particularly when present in greater proportion than tungsten (i.e., the Ta:W ratio is greater than 1). Furthermore, tantalum is an -tractive means of strength attainment in these alloys since it ij alieved not to directly participate in TCP phase formation. The molybdenum content is about 0.40-0.55% by weight. Advantageously, molybdenum is present in an amount of from 0.42% to 0.48% by weight. Molybdenum is a good solid solution strengthener, but it is not as effective as tungsten and tantalum, and it tends to be a negative factor toward hot corrosion capability. However, since the alloy's density is always a design consideration, and the molybdenum atom is lighter than the other solid solution strengtheners, the addition of molybdenum is a means of assisting control of the overall alloy density in the compositions of this invention. It is believed that the relatively low molybdenum content is unique in this class of bare hot corrosion resistant nickel-based single crystal superalloys. The aluminum content is about 3.4-3.8% by weight. Furthermore, the amount of aluminum present in these compositions is advantageously from 3.5% to 3.7% by weight. Aluminum and titanium are the primary elements comprising the gamma prime phase, and the sum of aluminum plus titanium in the present invention is from 7.4 to 8.2 percent by weight. These elements are added in these compositions in a proportion and ratio consistent with achieving adequate alloy castability, solution heat treatability, phasial stability and the desired blend of high mechanical strength and hot corrosion resistance. Aluminum is also added to these alloys in proportions sufficient to provide oxidation resistance. Tht4J.tanium content is about 4.0-4.4% by weight. Advantageously, 'titanium is present in this composition in an amount from 4.1% to 4.3% by weight. These alloys' titanium content is relatively high and, therefore, is beneficial to the alloys' hot corrosion resistance. However, it can also have a negative effect on oxidation resistance, alloy castability and alloy response to solution heat treatment. Accordingly, it is critical that the titanium content is maintained within the stated range of this composition and the proper balancing of the aforementioned elemental constituents is maintained. Furthermore, maintaining the alloys' Ti:Al ratio greater than 1 is critical in achieving the desired bare hot corrosion resistance in these compositions. The columbium content is about 0.05%-0.25% by weight and, advantageously, the columbium content is from 0.05% to 0.12% by weight. Columbium is a gamma prime forming element and it is an effective strengthener in the nickel-based superalloys of this invention. Generally, however, columbium is a detriment to alloy oxidation and hot corrosion properties, so its addition to the compositions of this invention is minimized. Moreover, columbium is added to this invention's compositions for the purpose of gettering carbon, which can be chemi-sorbed into component surfaces during non-optimized vacuum solution heat treatment procedures. Any carbon pick-up will tend to form columbium carbide instead of titanium or tantalum carbide, thereby preserving the greatest proportion of titanium and/or tantalum for gamma prime and/or solid solution strengthening in these alloys. Furthermore, it is critical that the sum of columbium plus hafnium is from 0.06 to 0.31 percent by weight in these compositions in order to enhance the strength of these superalloys. The hafnium content is about 0.01%-0.06% by weight and, advantageously, hafnium is present in an amount from 0.02% to 0.05% by weight. Hafnium is added in a small proportion to the present compositions in order to assist with coating performance and adherence. Hafnium generally partitions to the gamma prime phase. The balance of this invention's superalloy 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 composition so that they do not affect the advantageous aspects of the superalloy. For example, these incidental impurities may include up to about 0.05 percent carbon, up to about 0.03 percent boron, up to about 0.03 percent zirconium, up to about 0.25 percent rhenium, up to about 0.10 percent silicon, and up to about 0.10 percent manganese. Amounts of these impurities which exceed the stated amounts could have an adverse effect upon the resulting alloy's properties. Not only does the superalloy of this invention have a composition within the above specified ranges, but it also has a phasial stability number N^g less than about 2.45. As can be appreciated by those skilled in the art, NV3B 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 atonic percent: Atomic percent of element i = Pi = ^ - X100 where: Wi = weight percent of element i Ai « atomic weight of element i EQUATION 2 Calculation for the amount of each element present in the continuous matrix phase: (Equation Removed) EQUATION 3 Calculation of Nv3B using atomic factors from Equations 1 and 2 abov«i : (Equation Removed) where: each individual element in turn. N,i - the atomic factor of each element in matrix. (Nv)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) , the disclosure which is incorporated by reference herein. As can be appreciated by those skilled in the art, the phasial stability number for the superalloys 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, high stress 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 superalloys of this invention can be used to suitably make single crystal articles, such as components for industrial and marine gas turbine engines. Preferably, these superalloys are utilized to make a single crystal casting to be used under high stress, high temperature conditions characterized by an increased resistance to hot corrosion (sulfidation) under such conditions, particularly high temperature conditions involving corrosive atmospheres containing sulfur, sodium and vanadium contaminants, up to about 1922°F (1050°C). While these superalloys can be used for any purpose requiring high strength castings produced as a single crystal, their particular use is in the casting of single crystal blades and vanes for industrial and marine gas turbine engines. The single crystal components made from this invention's compositions can be produced by any of the single crystal casting techniques known in the art. For example, single crystal directional solidification processes can be utilized, such as the seed crystal process and the choke process. The single crystal castings made from the superalloys of the present invention can be aged at a temperature of from about 18000F (982°C) to about 2125°F (1163°C) for about 1 to about 50 hours. However, as can be appreciated by those skilled in the art, the optimum aging temperature and time for aging depends on the precise composition of the superalloy. This invention provides superalloy compositions having a unique blend of desirable properties. These properties include: excellent bare hot corrosion resistance and creep-rupture strength; good oxidation resistance; good single crystal component castability, particularly for large blade and vane components; good solution heat treatment response; adequate resistance to cast component recrystallization; adequate component coatability and microstructural stability, such as long-term resistance to the formation of undesirable, brittle phases called topologically close-packed (TCP) phases. As noted above, this superalloy has a precise composition with only small permissible variations in any one element if the unique blend of properties is to be maintained. In order to more clearly illustrate this invention and provide a comparison with representative superalloys outside the claimed scope of the invention, the examples set forth below are presented. The following examples are included as being illustrations of the invention and its relation to other superalloys and articles, and should not be construed as limiting the scope thereof. EXAMPLES Test materials were prepared to investigate the compositional variations and ranges for the superalloys of the present invention. Some of the alloy compositions tested and reported below fall outside the claimed scope of the present invention, but are included for comparative purposes to assist in the understanding of the invention. Representative alloy aim chemistries of materials tested are reported in Table 1 below. TABLE 1 (Table Removed) Single crystal alloy development to investigate the compositional variations for the superalloys of the present invention began with the definition and evaluation of a series of experimental compositions. The primary objective of the initial development effort was to achieve, with elemental balancing, a combination of increased hot corrosion resistance along with oxidation resistance, mechanical strength, large component castability, and adequate heat treatment response. The initial developmental alloy iteration, CMSX-11, was defined with the aim chemistry shown in Table 1 and was subsequently produced as a 250 Ib. (113 kg.) heat in a small production-type VIM furnace. (CMSX is a registered trademark of Cannon-Muskegon Corporation, assignee of the present application.) A small quantity of the resulting 3" (76 mm) diameter bar product from heat VF 839 (see Table 2 below) was investment cast to produce sixteen single crystal test bars. Grain and. orientation inspections revealed that only two bars exhibited rejectable grain or sliver indications. No freckles were apparent. Furthermore, all bars were within 15 of the desired primary (001) crystallographic orientation. TABLE 2 VIM FURNACE H"RVf CTTRMISTRIE8 (Table Removed)NOTE: Chemistries in wt. % unless otherwise indicated Solution heat treatment procedures developed for the alloy, having a peak temperature of 2305'F (1263C), resulted in complete coarse y' and eutectic y-y' solutioning. Following solution treatment, the bars were aged as reported in Table 3 below. TABLE 3 HEAT TREATMENT (Table Removed) Heat treated test bars were machined and low-stress ground to ASTM standard proportional specimen dimension for subsequent creep-rupture testing at various conditions of temperature and stress, according to standard ASTM procedure. Table 4 reported below shows the results of creep rupture tests undertaken with the CMSX-11 alloy specimens. The tests were performed at conditions ranging 1400 - 1800'F (760 - 982C), and the results indicated that this developmental alloy iteration was not as strong as desired. However, microstructural review of the failed rupture specimens revealed that this alloy iteration possessed adequate microstructural stability. TABLE 4 (Table Removed) The results of alloy hot corrosion tests undertaken concurrent to the creep-rupture evaluation are reported in Table 5 below. The initial burner rig test which was undertaken at 1650'F (899C), with 10 ppm sea salt ingestion and fuel containing approximately 1 ppm sulfur, was encouraging since it indicated that the alloy exhibited adequate corrosion resistance. However, the overall results of the test were not conclusive since the relatively low chromixim containing alloy, CMSX-3 alloy, exhibited surprisingly good resistance to attack relative to the CMSX-11 material. TABLE 5 (Table Removed) Following the aforementioned evaluations, a modified composition, designated CMSX-11A in Table 1, was derived and produced. Rather than producing another 250 Ib. (113 kg.) heat of the aim compositionf it was formulated during the investment casting process by melting/blending 22 Ibs. (10 kg.) of the VF 839 product with 4 Ibs. (1.8 kg.) of virgin elemental material. Sixteen each single crystal test bars were produced, with similar yields prevailing as achieved with CMSX-11 alloy. A test bar chemistry check indicated that adequate aim chemistry was attained. Full coarse y' and eutectic y~Y solutioning was achieved by using a peak soak temperature of 2293'F (1256'C). Test specimen aging treatments were applied as reported in Table 3 above, and several fully heat treated test bars were machined/ground to proportional creep test specimen dimension. Alloy strength was checked by subjecting the resulting test specimens to test conditions ranging 1400F - 1800F (760 -982C), The results are reported in Table 6 below. TABLE 6 (Table Removed) Failed test specimen microstructural review indicated that the CMSX-11A composition was a microstructurally unstable design based on varying levels of TCP sigma needle phase formation observed in some of the respective cross-sections. For this reason, plus the unacceptably low level of strength observed, the CMSX-11A composition was further modified in an attempt to achieve greater creep-rupture strength and improved phasial stability. With the CMSX-11A alloy NvJB phasial stability number calculated at 2.52 and the CMSX-11 test bar Nv3B phasial stablity nunber calculated at 2.39, the next compositional trial was aimed at achieving a 2.42 Nv3B level in order to obtain the desired strength level. Table 2 above reports the CMSX-11B aim composition. Since the Al + Ti level of the CMSX-llA composition allowed for complete solutioning, the CMSX-llB Al + Ti level was designed to remain "he same. Phasial stability was sought to be improved primarily v .uugh the reduction of Cr and Co, while the adequate solution heat treatment characteristic was fortified through further iduction of Cb alloying. Since it appeared that several more alloy iterations might be required before achieving the desired result, another approach was taken toward test specimen manufacture. This alternate approach consisted of manufacturing a lean base composition which could be used in varying combination with virgin elemental materials toward formulating CMSX-llB alloys with small chemistry differences. The resulting "lean-alloy" composition was designated R2D2 and a 250 Ib. (113 kg.) VIM heat, VF 952 (See Table 2 above), was produced. Twenty-three pounds of the R2D2 alloy composition was combined with three Ibs. of virgin elemental addition to produce the CMSX-llB aim composition reported in Table 1 above. A test bar chemistry check indicated adequate chemistry attainment. This particular mold produced thirteen each single crystal test bars along with three each, small single crystal turbine blades. Test bar and blade grain yield was 100%, while all Laue results showed the test specimens within 10* of the desired primary (001) crystallographic orientation. Concurrent to this, quantities of VF 952 + virgin elemental addition (to produce CMSX-11B alloy) were investment cast to produce twelve single crystal test bars and twelve single crystal blades. All the molds used to produce these products exhibited 100% grain yield and all the specimens were controlled to within 5* of the desired primary (001) crystallographic orientation. A chemistry check of the CMSX-11B test materials after they were investment cast revealed that adequate chemistry attainment was achieved. Solution heat treatment trials revealed that the materials could be 100% solutioned when given a final soak at 2300'F (1260'C) . Following solution treatment, several test bar specimens were utilized to determine the effect of varied primary aging treatment. This investigation indicated that a 5 hour soak at 2050F (1121'C) resulted in a more preferred arrangement and optimally sized (approximately 0.5 ^m) y' precipitate than the previously employed primary age at 1975F (1079C)/4 Hr./AC. Lower temperature aging remained the same as previously employed, which is detailed in Table 3 above. Moderate quantities of CMSX-11B test bars and test blades were prepared for creep-rupture testing. They were fully heat treated as detailed in Table 3 above. Longitudinal proportional creep specimens, generally 0.125" gage diameter, were prepared with the "i ;i^ crystal test bars, while longitudinal airfoil and -iansverse root section specimens of 0.070" gage diameter were extracted from the test blades. The specimens were subjected to stress-and creep-rupture testing at temperature ranging 1400 - 1800'F (760 - 982'C). Since the initial results of these tests were encouraging, the testing program was expanded to include temperature/stress conditions up to 1900'F (1038'C). The results of these tests are reported in Table 7 below. TABLE 7 STRESS - AND CREEP-RUPTURE DATA (Table Removed) With the stress-and creep-rupture results continuing to be favorable, two more 250 Ib. (113 kg.) VIM heats of the CMSX-11B composition were produced. The heat identities for the two heats are VF 999 and VG 32, and their respective compositions are detailed in Table 2. Material from these heats was then used to produce additional investment cast test bars and blades. A chemistry check of the test materials indicated adequate chemistry attainment. Perfect single crystal grain yield prevailed for some of this product, and heat treat processing of the specimens yielded similar results; to previous experience. Further mechanical property testing was undertaken with some of the test product, the results of which are reported in Table 7 above. Concurrent to this activity, fully heat treated specimens of CMSX-11B alloy were subjected to oxidation and hot corrosion testing. The results of hot corrosion tests performed are presented in Table 8 below. The tests were undertaken at 700C (1292'F) and 800C (1472F) in a laboratory furnace utilizing an artificial ash plus S02. Metal loss data are reported as mean and maximum values, as well as a percentage loss of the test pin employed. Data are reported for intervals of 100, 576 and 1056 hours for the 700'C (1292'F) test, and 100, 576, 1056 and 5000 hours for the 800'C (1472'F) test. TABLE 8 (Table Removed) Similarly, Figure 1 illustrates the results of additional hot corrosion tests undertaken with CMSX-ilB alloy and other alloys to 500 hours exposure in synthetic slag (GTV Type) plus .03 volume percent SOX in air. The 500 hour tests were undertaken at 750, 850 and 900'C (1382, 1562, 1652'F). These results indicate that the CMSX-11B alloy provides extremely good corrosion resistance at all three test temperatures. Subsequent testing utilizing an alternative slag, type FW, with test temperatures of 800C and 900'C (1472, 1652F), was also undertaken. The 500 hour test results are reported in Table 9 below. TABLE 9 CKSI-11B ALLOY vs. IN 738 LC XLLOY EOT CORROSION Results presented represent depth of penetration after 500 hours exposure in synthetic slag (type FW) plus 0.03% SOX in air. • Test Temperature — 800'C (1472F) Alloy Maximum Penetration Average Penetration CMSX-11B 350 Mm 170 Mm Test Temperature — 900C (1652'F) Alloy Maximum Penetration Average Penetration CMSX-11B 220 Mm 150 Mm IN 738 LC 190 Mm Additional laboratory furnace, crucible type, artificial ash hot corrosion tests were performed. The results of these tests, undertaken at 732'C (1350'F) and 899'C (1650'F), are illustrated in Figures 2 and 3, respectively. In these tests, the specimens were coated with 1 mg./cm2 Na2S04 every 100 cycles and were cycled 3 times per day. The test at 732 C was run to about 2400 hours while the one at 899 C was taken to about 1800 hours. Further hot corrosion tests were performed with the CMSX-11B alloy. In contrast to the aforementioned tests, the hot corrosion evaluations subsequently undertaken were performed in burner rigs, which is usually a preferred method of testing since the results achieved in burner rig tests generally give more representative indications of the way materials will perform in a gas turbine engine. The burner rig tests were performed at 900 C (1652F) and 1050C (1922F), and the test results are reported below in Tables 10 and 11, respectively. The 9 mm diameter x 100 mm long test pins utilized were mounted in a rotating cylindrical jig and exposed to a high speed gas stream. Other test conditions are specified in the respective Tables. TABLE 10 (Table Removed) TABLE 11 1050'C (1922F) HOT CORROSION (BURNER RIG.) Weight Loss In Grams As a Function of Ttae (Table Removed) Several alloys were evaluated within the same rig. The results indicate that CMSX-11B alloy provided much better hot corrosion resistance than IN 738 LC alloy at the 900C (1652F) test condition and similar capability at 1050'C (1922T). Furthermore, Figure 4 illustrates that CMSX-11B alloy provides an attractive blend of strength and hot corrosion resistance at 1050'C (1922F). It is believed that a similar analysis at 900'C would illustrate an even greater blend of capability. CMSX-11B alloy oxidation tests were performed concurrent to the hot corrosion tests. Table 12 below reports the results of a laboratory furnace oxidation test performed at 950'C (1742T) for 1000 hour duration. Mean and maximum oxidation depth plus weight gain measurements undertaken at 100 and 500 hour intervals are reported, as well as at test completion. TABLE 12 (Table Removed) Figure 5 illustrates the results of 1000'C (1832T) oxidation tests run to as long as 3000 hours. The tests which were performed in an air atmosphere, and measured test specimen weight change as a function of time. The test temperature was cycled to room temperature on a once-per-hour basis. The test results indicate that the CMSX-llB alloy provides much better oxidation resistance than IN 738 LC, an alloy which is widely used throughout the industrial turbine industry. Further oxidation test results are illustrated in Figure 6. In this particular test, the pins were cycled to room temperature 3 times per day from the 1010C (1850'F) test temperature and weight change measured as a function of time. The test was run to about 2400 hours and the results indicate that the CMSX-llB material provides much better oxidation resistance than the alloy IN 738. Burner rig oxidation testing was undertaken at 1200C (2192F), with the results presented in Table 13 below. Various alloys were tested within the same rotating carousel and specimen weight loss was measured at intervals of 100, 200, 300, 400 and 500 hours. Additional test conditions are provided in the Table. TABLE 13 1200C (2192F) OXIDATION (BURNER RIG.) Weight Less In Graas As a Fine tier ef time (Table Removed)The burner rig oxidation test results illustrate that the CMSX-11B material provides extremely good 1200'C (2192F) oxidation resistance in comparison to widely used industrial turbine blade and vane materials. An alloy strength and 1200C (2192F) oxidation comparison is illustrated in Figure 7. This Figure illustrates that the CMSX-11B alloy blended capability is superior to directional solidified alloys such as Rene 80 H, FSX 414, IN 939 and IN 738 LC alloys. Additional small VIM heats of the CMSX-11B alloy were produced subsequent to the aforementioned tests. The aim compositions for the CMSX-11B1 and CMSX-11B" materials are reported in Table 1 above. These compositions were produced in order to explore the effects of small changes in the CMSX-11B alloy design. The chemistries achieved for the 270 Ib. (122 kg.) heats produced are reported in Table 2 above, and identified with the respective heat numbers of VG 92 and VG 109. Quantities of these respective heats were investment cast to manufacture single crystal test bars. A chemistry check of the resulting bars indicated that adequate chemistry attainment was realized. Respective single cr tal grain and orientation yields were 100% satisfactory, as experienced with the earlier alloy iterations. Heat treatment trials led to the selection of a peak solution temperature of 1264"C (2307'F) for both alloys, as reported in Table 3 above. This resulted in solution levels of 99.5 - 100%. Aging treatments were applied as developed for CMSX-11B alloy. Specimens were prepared for creep-rupture testing, and tests were undertaken at temperature ranging 760 - 1038'C (1400'F - 1900'F). These test results are reported in Table 7 above, and appear to be improved relative to the CMSX-11B experience. 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 true spirit and scope of the present information. WE CLAIM ;- 1. A process for manufacturing a hot corrosion resistant nickel-based superalloy composition comprising mixing and melting the following elements in percent by weight: Chromium about 11.5-13.5 Cobalt about 5.5-8.5 Molybdenum about 0.40-0.55 Tungsten about 4.5-5.5 Tantalum about 4.5-5.8 Columbium about 0.05-0.25 Aluminum about 3.4-3.8 Titanium about 4.0-4.4 Hafnium about 0.01-0.06 Nickel + Incidental balance Impurities Carbon about 0-0.05 Boron about 0-0.03 Zirconium about 0-0.03 Rhenium about 0-0.25 Silicon about 0-0.10 Manganese about 0-0.10 and cooling to obtain said superalloy composition having a phasial stability number Ny^g less than about 2.45. 2 . A process for manufacturing a superalloy composition as claimed in claim 1, wherein the sum of columbium plus hafnium is from 0.06 to 0.31 percent by weight. 3. A process for manufacturing a superalloy composition as claimed in claim 1, wherein the Ti:Al ratio is greater than 1. 4. A process for manufacturing a superalloy composition as claimed in claim 1, wherein the sum of aluminum plus titanium is from 7.4 to 8.2 percent by weight. 5. A process for manufacturing a superalloy composition as claimed in claim 1, wherein the Ta:W ratio is greater than 1. 6. A process for manufacturing a superalloy composition as claimed in claim 1, wherein the said superalloy composition has an increased resistance to oxidation. 7 - A process for manufacturing a hot corrosion resistant nickel-based superalloy composition, substantially as hereinbefore described with reference to the accompanying drawings.

Full Text

1. Field of the Invention
This invention relates to single crystal nickel-based superalloys and, more particularly, single crystal nickel-based superalloys and articles made therefrom having increased resistance to bare hot corrosion for use in gas turbine engines.
2. Description of the Prior Art
Advances over recent years in the metal temperature and stress capability of single crystal articles have been the result of the continuing development of single crystal superalloys, as well as improvements in casting processes and engine application technology. These single crystal superalloy articles include rotating and stationary turbine blades and vanes found in the hot sections of gas turbine engines. Gas turbine engine design goals have remained the same during the past decades. These goals include the desire to increase engine operating temperature, rotational speed, fuel efficiency, and engine component durability and reliability.
Prior art attempts to provide alloys to help achieve these design goals for industrial gas turbine engine applications include U.S. Patent No. 4,677,035, Fiedler et al., which
discloses a nickel-base single crystal alloy composition consisting essentially of, in percent by weight, 8.0-14.0% c romium, 1.5-6.0% cobalt, 0.5-2.0% molybdenum, 3.0-10.0% u^..*g~ten, 2.5-7.0% titanium, 2.5-7.0% aluminum, 3.0-6.0% tan* Mm, and the balance nickel. However, the alloy compositions taught by this reference, while possessing relatively high strength at prolonged or repeated exposure to high temperatures, are susceptible to the accelerated corrosive effect of the hot gas environment in which components fabricated from the alloys are exposed to when used in gas turbines.
Also, U.K. Patent Application Publication No. 2153848A discloses nickel-base alloys having a composition within the range of 13-15.6% chromium, 5-15% cobalt, 2.5-5% molybdenum, 3-6% tungsten, 4-6% titanium, 2-4% aluminum, and the balance essentially nickel without intentional additions of carbon, boron or zirconium, which are fabricated into single crystals. Although the alloys taught by this reference claim an improvement in hot corrosion resistance accompanied by an increase in creep rupture properties, the need remains in the art for single crystal superalloys for industrial gas turbine applications having a superior combination of increased hot corrosion resistance, oxidation resistance, mechanical strength, large component castability and adequate heat treatment response.
Single crystal articles are gemarally produced having the low-modulus (001) crystallographic orientation parallel to the component dendritic growth pattern or blade stacking axis. Face-centered cubic (FCC) superalloy single crystals grown in the (001) direction provide extremely good thermal fatigue resistance relative to conventionally cast polycrystalline articles. Since these single crystal articles have no grain boundaries, alloy design without grain boundary strengtheners, such as carbon, boron aind zirconium, is possible. As these elements are alloy melting point depressants, their essential elimination from the alloy design provides a greater potential for high temperature mechanical strength achievement since more complete gamma prime solution and microstructural homogenization can be achieved relative to directionally solidified (DS) columnar grain and conventionally cast materials, made possible by a higher incipient melting temperature.
These process benefits are not necessarily realized unless a multi-faceted alloy design approach is undertaken. Alloys must be designed to avoid tendency for casting defect formation such as freckles, slivers, spurious grains and recrystalllzation, particularly when utilized for large cast components. Additionally, the alloys must provide an adequate heat treatment "window" (numeric difference between an alloy's gamma prime solvus and incipient melting point) to allow for nearly complete gamma prime solutioning. At the same time, the
alloy compositional balance should be designed o ~, ..vide an adequate blend of engineering properties nec*r-sar • for operation in gas turbine engines. Selected properties jer orally considered important by gas turbine engine designers incl 'da: elevated temperature creep-rupture strength, thermo-mechanical fatigue resistance, impact resistance, hot corrosion and oxidation resistance, plus coating performance. In particular, industrial turbine designers require unique blends of hot corrosion and oxidation resistance, plus good long-term mechanical properties.
An alloy designer can attempt to improve one or two of these design properties by adjusting the compositional balance of known superalloys. However, it is extremely difficult to improve more than one or two of the design properties without significantly or even severely compromising some of the remaining properties. The unique superalloy of the present invention provides an excellent blend of the properties necessary for use in producing single crystal articles for operation in industrial and marine gas turbine engine hot sections.
SUMMARY OF THE INVENTION
This invention relates to a hot corrosion resistant nickel-based superalloy comprising the following elements in percent by weight: from about 11.5 to about 13.5 percent chromium, from about 5.5 to about 8.5 percent cobalt, from about
0.40 to about 0.55 perosnt molybdenum, from about 4.5 to about
5 percent tungsten, froifr about 4.5 ^to about 5.8 percent -antalum, from about 0.^5 co about 0.25 percent columbium, from about 3.4 to about 3.8 percent aluminum, from about 4.0 to about 4.4 percent titanium, from about 0.01 to about 0.06 percent hafnium, and the balance nickel plus incidental impurities, the superalloy having a phasial stability number N^g less than about 2.45.
Advantageously, the sum of aluminum plus titanium in this superalloy composition is from 7.4 to 8.2 percent by weight. Also, it is advantageous to have a Ti:Al ratio greater than 1 and a Ta:W ratio greater than 1 in the composition of the present invention. Although incidental impurities should be kept to the least amount possible, the superalloy can also be comprised of from about 0 to about 0.05 percent carbon, from about 0 to about 0.03 percent boron, from about 0 to about 0.03 percent zirconium, from about 0 to about 0.25 percent rhenium, from about 0 to about 0.10 percent silicon, and from about 0 to about 0.10 percent manganese. In all cases, the base element is nickel. This invention provides a single crystal superalloy having an increased resistance to hot corrosion, an increased resistance to oxidation, and increased creep-rupture strength.
Single crystal articles can be suitably made from the superalloy of this invention. The article can be a component for
a gas turbine engine and, more particularly, the component can be a gas turbine blade or gas turbine vane.
The superalloy compositions of this invention have a critically balanced alloy chemistry which results in a unique blend of desirable properties, including an increased resistance to hot corrosion, which are particularly suitable for industrial and marine gas turbine applications. These properties include: excellent bare hot corrosion resistance and creep-rupture strength; good bare oxidation resistance; good single crystal component castability, particularly for large blade and vane components; good solution heat treatment response; adequate resistance to cast component recrystallization; adequate component coatability and microstructural stability, such as long-term resistance to the formation of undesirable, brittle phases called topologically close-packed (TCP) phases.
Accordingly, it is an object of the present to provide superalloy compositions and single crystal articles made therefrom having a unique blend of desirable properties, including increased hot corrosion resistance. It is a further object of the present invention to provide superalloys and single crystal articles made therefrom for use in industrial and marine gas turbine engines. These and other objects and advantages of the present invention will be apparent to those skilled in the art upon reference to the following description of the preferred
-8-
embodiments .
According to the- present invention relates to a process for manufacturing a hot corrosion resistant nickel -based superalloy composition comprising mixing and melting the following elements in percent by weight:
Chromium about 11.5-13.5
Cobalt about 5.5-8.5
Molybdenum about 0.40-0.55
Tungsten about 4.5-5.5
Tantalum about 4.5-5.8
Columbium about 0.05-0.25
Aluminum about 3.4-3.8
Titanium about 4.0-4.4
Hafnium about 0.01-0.06
Nickel + Incidental balance
Impurities
Carbon about 0-0.05
Boron about 0-0.03
Zirconium about 0-0.03
Rhenium about 0-0.25
Silicon about 0-0.10
Manganese about 0-0.10
and cooling to obtain said superalloy composition having a phasial stability number N- less than about 2.45.
The composition resulting from the process is not a mere admixture but a synergistic composition where all the components are not reacting but are interacting with each other to show unexpected properties.

embodiments.
BRIEF DESCRIPTION OF THE/DRAWINGS
V FIG. 1 is a chart of hot corrosion test results performed at three exposure temperatures on one embodiment of this invention and on four other alloys.
FIG. 2 is a graphical comparison of hot corrosion data from tests performed at 732°C (1350°F) on one embodiment of this invention and on two other alloys.
FIG. 3 is a graphical comparison of hot corrosion data from tests performed at 899°C (1650°F) on one embodiment of this invention and on two other alloys.
FIG. 4 is a graphical comparison of alloy strength and hot corrosion data from tests performed on one embodiment of this invention and on six other alloys.
FIG. 5 is a graphical comparison of oxidation data from tests performed at 1000°C (1832°F) on one embodiment of this invention and on two other alloys.
FIG. 6 is a graphical comparison of oxidation data from
tests performed at 1010°C (1850°F) on one embodiment of the present invention and on two other alloys.
FIG. 7 is a graphical comparison of alloy strength and oxidation data from tests performed on one embodiment of this invention and on six other alloys.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The hot corrosion resistant nickel-based superalloy of the present invention comprises the following elements in percent by weight:
'Chromium Cobalt Molybdenum Tungsten Tantalum Columbium Aluminum Titanium Hafnium
Nickel + Incidental Impurities
about 11.5-13.5 about 5.5-8.5 about 0.40-0.55 about 4.5-5.5 about 4.5-5.8 about 0.05-0.25 about 3.4-3.8 about 4.0-4.4 about 0.01-0.06 balance
This superalloy composition also has a phasial stability number
less than about 2.45. Further, this invention has a
critically balanced alloy chemistry which results in a unique blend of desirable properties useful for industrial and marine
gas turbine engine applications. These properties include a superior blend of bare hot corrosion resistance and creep-rupture strength relative to prior art single crystal superalloys for industrial and marine gas turbine applications, bare oxidation resistance, single crystal component castability, and microstructural stability, including resistance to TCP phase formation under high stress, high temperature conditions.
Superalloy chromium content is a primary contributor toward attaining superalloy hot corrosion resistance. The supsralioys of the present invention have a relatively high chromium content since alloy hot corrosion resistance was one of the primary design criteria in the development of these alloys. The chromium is about 11.5-13.5% by weight. Advantageously, the chromium content is from 12.0% to 13.0% by weight. Although chromium provides hot corrosion resistance, it may also assist with the alloys' oxidation capability. Additionally, this superalloys' tantalum and titanium contents, as well as its Ti:Al ratio being greater than 1, are beneficial for hot corrosion resistance attainment. However, besides lowering the alloys' gamma prime solvus, chromium contributes to the formation of Cr and W-rich TCP phase and must be balanced accordingly in these compositions.
In one embodiment of the present invention, the cobalt content is about 5.5-8.5% by weight. In another embodiment of
the present invention, the cobalt content is from 6.2% to 6.8% by weight. The chromium and cobalt levels in these superalloys assist in making the superalloy solution heat treatable, since both elements tend to decrease an alloy's gamma prime solvus. Proper balancing of these elements in the present invention in tandem with those which tend to increase the alloy's incipient melting temperature, such as tungsten and tantalum, result in superalloy compositions which have desirable solution heat treatment windows (numerical difference between an alloy's incipient melting point and its gamma prime solvus), thereby facilitating full gamma prime solutioning. The cobalt content is also beneficial to the superalloy's solid solubility.
The tungsten content is about 4.5-5.5% by weight and, advantageously, the amount of tungsten is from 4.7% to 5.3% by weight, Tungsten is added in these compositions since it is an effective solid solution strengthener and it can contribute to strengthening the gamma prime. Additionally, tungsten is effective in raising the alloy's incipient melting temperature.
Similar to tungsten, tantalum is a significant solid solution strengthener in these compositions, while also contributing to enhanced gamma prime particle strength and volume fraction. The tantalum content is about 4.5-5.8% by weight and, advantageously,, the tantalum content is from 4.9% to 5.5% by weight. In these compositions, tantalum is beneficial since it
helps to provide bare hot corrosion and oxidation resistance, along with aluminide coating durability. Additionally, tantalum is an extractive single crystal alloy additive in these compositions since it assists in preventing "freckle" defect formation during the single crystal casting process particularly when present in greater proportion than tungsten (i.e., the Ta:W ratio is greater than 1). Furthermore, tantalum is an
-tractive means of strength attainment in these alloys since it ij alieved not to directly participate in TCP phase formation.
The molybdenum content is about 0.40-0.55% by weight. Advantageously, molybdenum is present in an amount of from 0.42% to 0.48% by weight. Molybdenum is a good solid solution strengthener, but it is not as effective as tungsten and tantalum, and it tends to be a negative factor toward hot corrosion capability. However, since the alloy's density is always a design consideration, and the molybdenum atom is lighter than the other solid solution strengtheners, the addition of molybdenum is a means of assisting control of the overall alloy density in the compositions of this invention. It is believed that the relatively low molybdenum content is unique in this class of bare hot corrosion resistant nickel-based single crystal superalloys.
The aluminum content is about 3.4-3.8% by weight. Furthermore, the amount of aluminum present in these compositions
is advantageously from 3.5% to 3.7% by weight. Aluminum and titanium are the primary elements comprising the gamma prime phase, and the sum of aluminum plus titanium in the present invention is from 7.4 to 8.2 percent by weight. These elements are added in these compositions in a proportion and ratio consistent with achieving adequate alloy castability, solution heat treatability, phasial stability and the desired blend of high mechanical strength and hot corrosion resistance. Aluminum is also added to these alloys in proportions sufficient to provide oxidation resistance.
Th*t4J.tanium content is about 4.0-4.4% by weight. Advantageously, 'titanium is present in this composition in an amount from 4.1% to 4.3% by weight. These alloys' titanium content is relatively high and, therefore, is beneficial to the alloys' hot corrosion resistance. However, it can also have a negative effect on oxidation resistance, alloy castability and alloy response to solution heat treatment. Accordingly, it is critical that the titanium content is maintained within the stated range of this composition and the proper balancing of the aforementioned elemental constituents is maintained. Furthermore, maintaining the alloys' Ti:Al ratio greater than 1 is critical in achieving the desired bare hot corrosion resistance in these compositions.
The columbium content is about 0.05%-0.25% by weight
and, advantageously, the columbium content is from 0.05% to 0.12% by weight. Columbium is a gamma prime forming element and it is an effective strengthener in the nickel-based superalloys of this invention. Generally, however, columbium is a detriment to alloy oxidation and hot corrosion properties, so its addition to the compositions of this invention is minimized. Moreover, columbium is added to this invention's compositions for the purpose of gettering carbon, which can be chemi-sorbed into component surfaces during non-optimized vacuum solution heat treatment procedures. Any carbon pick-up will tend to form columbium carbide instead of titanium or tantalum carbide, thereby preserving the greatest proportion of titanium and/or tantalum for gamma prime and/or solid solution strengthening in these alloys. Furthermore, it is critical that the sum of columbium plus hafnium is from 0.06 to 0.31 percent by weight in these compositions in order to enhance the strength of these superalloys.
The hafnium content is about 0.01%-0.06% by weight and, advantageously, hafnium is present in an amount from 0.02% to 0.05% by weight. Hafnium is added in a small proportion to the present compositions in order to assist with coating performance and adherence. Hafnium generally partitions to the gamma prime phase.
The balance of this invention's superalloy 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 composition so that they do not affect the advantageous aspects of the superalloy. For example, these incidental impurities may include up to about 0.05 percent carbon, up to about 0.03 percent boron, up to about 0.03 percent zirconium, up to about 0.25 percent rhenium, up to about 0.10 percent silicon, and up to about 0.10 percent manganese. Amounts of these impurities which exceed the stated amounts could have an adverse effect upon the resulting alloy's properties.
Not only does the superalloy of this invention have a composition within the above specified ranges, but it also has a phasial stability number N^g less than about 2.45. As can be appreciated by those skilled in the art, NV3B 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 atonic percent:
Atomic percent of element i = Pi = ^ - X100
where: Wi = weight percent of element i Ai « atomic weight of element i
EQUATION 2
Calculation for the amount of each element present in the continuous matrix phase:

(Equation Removed)
EQUATION 3
Calculation of Nv3B using atomic factors from Equations 1 and 2
abov«i :
(Equation Removed)
where: each individual element in turn.
N,i - the atomic factor of each element in matrix.
(Nv)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) , the disclosure which is incorporated by reference herein. As can be appreciated by those skilled in the art, the phasial stability number for the superalloys 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, high stress 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 superalloys of this invention can be used to suitably make single crystal articles, such as components for industrial and marine gas turbine engines. Preferably, these superalloys are utilized to make a single crystal casting to be used under high stress, high temperature conditions characterized by an increased resistance to hot corrosion (sulfidation) under such conditions, particularly high temperature conditions involving corrosive atmospheres containing sulfur, sodium and vanadium contaminants, up to about 1922°F (1050°C). While these superalloys can be used for any purpose requiring high strength castings produced as a single crystal, their particular use is in the casting of single crystal blades and vanes for industrial and marine gas turbine engines.
The single crystal components made from this
invention's compositions can be produced by any of the single crystal casting techniques known in the art. For example, single crystal directional solidification processes can be utilized, such as the seed crystal process and the choke process.
The single crystal castings made from the superalloys of the present invention can be aged at a temperature of from about 18000F (982°C) to about 2125°F (1163°C) for about 1 to about
50 hours. However, as can be appreciated by those skilled in the art, the optimum aging temperature and time for aging depends on the precise composition of the superalloy.
This invention provides superalloy compositions having a unique blend of desirable properties. These properties include: excellent bare hot corrosion resistance and creep-rupture strength; good oxidation resistance; good single crystal component castability, particularly for large blade and vane components; good solution heat treatment response; adequate resistance to cast component recrystallization; adequate component coatability and microstructural stability, such as long-term resistance to the formation of undesirable, brittle phases called topologically close-packed (TCP) phases. As noted above, this superalloy has a precise composition with only small permissible variations in any one element if the unique blend of properties is to be maintained.
In order to more clearly illustrate this invention and provide a comparison with representative superalloys outside the claimed scope of the invention, the examples set forth below are presented. The following examples are included as being illustrations of the invention and its relation to other superalloys and articles, and should not be construed as limiting the scope thereof.
EXAMPLES
Test materials were prepared to investigate the compositional variations and ranges for the superalloys of the present invention. Some of the alloy compositions tested and reported below fall outside the claimed scope of the present invention, but are included for comparative purposes to assist in the understanding of the invention. Representative alloy aim chemistries of materials tested are reported in Table 1 below.
TABLE 1
(Table Removed)
Single crystal alloy development to investigate the compositional variations for the superalloys of the present invention began with the definition and evaluation of a series of experimental compositions. The primary objective of the initial development
effort was to achieve, with elemental balancing, a combination of increased hot corrosion resistance along with oxidation resistance, mechanical strength, large component castability, and adequate heat treatment response.
The initial developmental alloy iteration, CMSX*-11, was defined with the aim chemistry shown in Table 1 and was subsequently produced as a 250 Ib. (113 kg.) heat in a small production-type VIM furnace. (CMSX is a registered trademark of Cannon-Muskegon Corporation, assignee of the present application.) A small quantity of the resulting 3" (76 mm) diameter bar product from heat VF 839 (see Table 2 below) was investment cast to produce sixteen single crystal test bars. Grain and. orientation inspections revealed that only two bars exhibited rejectable grain or sliver indications. No freckles were apparent. Furthermore, all bars were within 15* of the desired primary (001) crystallographic orientation.
TABLE 2 VIM FURNACE H"RVf CTTRMISTRIE8
(Table Removed)NOTE: Chemistries in wt. % unless otherwise indicated
Solution heat treatment procedures developed for the alloy, having a peak temperature of 2305'F (1263*C), resulted in complete coarse y' and eutectic y-y' solutioning. Following solution treatment, the bars were aged as reported in Table 3 below.
TABLE 3 HEAT TREATMENT

(Table Removed)
Heat treated test bars were machined and low-stress ground to ASTM standard proportional specimen dimension for subsequent creep-rupture testing at various conditions of temperature and stress, according to standard ASTM procedure.
Table 4 reported below shows the results of creep rupture tests undertaken with the CMSX-11 alloy specimens. The tests were performed at conditions ranging 1400 - 1800'F (760 - 982*C), and the results indicated that this developmental alloy iteration was not as strong as desired. However, microstructural review of the failed rupture specimens revealed that this alloy iteration possessed adequate microstructural stability.
TABLE 4
(Table Removed)
The results of alloy hot corrosion tests undertaken concurrent to the creep-rupture evaluation are reported in Table 5 below. The initial burner rig test which was undertaken at 1650'F (899*C), with 10 ppm sea salt ingestion and fuel containing approximately 1 ppm sulfur, was encouraging since it indicated that the alloy exhibited adequate corrosion resistance. However, the overall results of the test were not conclusive since the relatively low chromixim containing alloy, CMSX-3 alloy, exhibited surprisingly good resistance to attack relative to the CMSX-11 material.
TABLE 5
(Table Removed)
Following the aforementioned evaluations, a modified composition, designated CMSX-11A in Table 1, was derived and produced. Rather than producing another 250 Ib. (113 kg.) heat of the aim
compositionf it was formulated during the investment casting process by melting/blending 22 Ibs. (10 kg.) of the VF 839 product with 4 Ibs. (1.8 kg.) of virgin elemental material.
Sixteen each single crystal test bars were produced, with similar yields prevailing as achieved with CMSX-11 alloy. A test bar chemistry check indicated that adequate aim chemistry was attained. Full coarse y' and eutectic y~Y* solutioning was achieved by using a peak soak temperature of 2293'F (1256'C). Test specimen aging treatments were applied as reported in Table 3 above, and several fully heat treated test bars were machined/ground to proportional creep test specimen dimension. Alloy strength was checked by subjecting the resulting test specimens to test conditions ranging 1400*F - 1800*F (760 -982*C), The results are reported in Table 6 below.
TABLE 6
(Table Removed)
Failed test specimen microstructural review indicated that the CMSX-11A composition was a microstructurally unstable design based on varying levels of TCP sigma needle phase formation observed in some of the respective cross-sections. For this reason, plus the unacceptably low level of strength observed, the CMSX-11A composition was further modified in an attempt to achieve greater creep-rupture strength and improved phasial stability.
With the CMSX-11A alloy NvJB phasial stability number calculated at 2.52 and the CMSX-11 test bar Nv3B phasial stablity nunber calculated at 2.39, the next compositional trial was aimed at achieving a 2.42 Nv3B level in order to obtain the desired strength level.
Table 2 above reports the CMSX-11B aim composition. Since the Al
+ Ti level of the CMSX-llA composition allowed for complete solutioning, the CMSX-llB Al + Ti level was designed to remain *"he same. Phasial stability was sought to be improved primarily v .uugh the reduction of Cr and Co, while the adequate solution heat treatment characteristic was fortified through further iduction of Cb alloying.
Since it appeared that several more alloy iterations might be required before achieving the desired result, another approach was taken toward test specimen manufacture. This alternate approach consisted of manufacturing a lean base composition which could be used in varying combination with virgin elemental materials toward formulating CMSX-llB alloys with small chemistry differences. The resulting "lean-alloy" composition was designated R2D2 and a 250 Ib. (113 kg.) VIM heat, VF 952 (See Table 2 above), was produced.
Twenty-three pounds of the R2D2 alloy composition was combined with three Ibs. of virgin elemental addition to produce the CMSX-llB aim composition reported in Table 1 above. A test bar chemistry check indicated adequate chemistry attainment. This particular mold produced thirteen each single crystal test bars along with three each, small single crystal turbine blades. Test bar and blade grain yield was 100%, while all Laue results showed the test specimens within 10* of the desired primary (001) crystallographic orientation.
Concurrent to this, quantities of VF 952 + virgin elemental addition (to produce CMSX-11B alloy) were investment cast to produce twelve single crystal test bars and twelve single crystal blades. All the molds used to produce these products exhibited 100% grain yield and all the specimens were controlled to within 5* of the desired primary (001) crystallographic orientation.
A chemistry check of the CMSX-11B test materials after they were investment cast revealed that adequate chemistry attainment was achieved. Solution heat treatment trials revealed that the materials could be 100% solutioned when given a final soak at 2300'F (1260'C) .
Following solution treatment, several test bar specimens were utilized to determine the effect of varied primary aging treatment. This investigation indicated that a 5 hour soak at 2050*F (1121'C) resulted in a more preferred arrangement and optimally sized (approximately 0.5 ^m) y' precipitate than the previously employed primary age at 1975*F (1079*C)/4 Hr./AC. Lower temperature aging remained the same as previously employed, which is detailed in Table 3 above.
Moderate quantities of CMSX-11B test bars and test blades were prepared for creep-rupture testing. They were fully heat treated as detailed in Table 3 above. Longitudinal proportional creep specimens, generally 0.125" gage diameter, were prepared with the
"i ;i^ crystal test bars, while longitudinal airfoil and -iansverse root section specimens of 0.070" gage diameter were extracted from the test blades.
The specimens were subjected to stress-and creep-rupture testing at temperature ranging 1400 - 1800'F (760 - 982'C). Since the initial results of these tests were encouraging, the testing program was expanded to include temperature/stress conditions up to 1900'F (1038'C). The results of these tests are reported in Table 7 below.
TABLE 7
STRESS - AND CREEP-RUPTURE DATA
(Table Removed)
With the stress-and creep-rupture results continuing to be favorable, two more 250 Ib. (113 kg.) VIM heats of the CMSX-11B composition were produced. The heat identities for the two heats are VF 999 and VG 32, and their respective compositions are detailed in Table 2.
Material from these heats was then used to produce additional investment cast test bars and blades. A chemistry check of the test materials indicated adequate chemistry attainment. Perfect single crystal grain yield prevailed for some of this product, and heat treat processing of the specimens yielded similar results; to previous experience.
Further mechanical property testing was undertaken with some of the test product, the results of which are reported in Table 7 above. Concurrent to this activity, fully heat treated specimens of CMSX-11B alloy were subjected to oxidation and hot corrosion testing.
The results of hot corrosion tests performed are presented in Table 8 below. The tests were undertaken at 700*C (1292'F) and 800*C (1472*F) in a laboratory furnace utilizing an artificial ash plus S02. Metal loss data are reported as mean and maximum values, as well as a percentage loss of the test pin employed. Data are reported for intervals of 100, 576 and 1056 hours for the 700'C (1292'F) test, and 100, 576, 1056 and 5000 hours for the 800'C (1472'F) test.

TABLE 8

(Table Removed)
Similarly, Figure 1 illustrates the results of additional hot corrosion tests undertaken with CMSX-ilB alloy and other alloys to 500 hours exposure in synthetic slag (GTV Type) plus .03 volume percent SOX in air. The 500 hour tests were undertaken at 750, 850 and 900'C (1382, 1562, 1652'F). These results indicate that the CMSX-11B alloy provides extremely good corrosion resistance at all three test temperatures.
Subsequent testing utilizing an alternative slag, type FW, with test temperatures of 800*C and 900'C (1472, 1652*F), was also undertaken. The 500 hour test results are reported in Table 9 below.
TABLE 9 CKSI-11B ALLOY vs. IN 738 LC XLLOY EOT CORROSION
Results presented represent depth of penetration after 500 hours exposure in synthetic slag (type FW) plus 0.03% SOX in air.
• Test Temperature — 800'C (1472*F)
Alloy Maximum Penetration Average Penetration
CMSX-11B 350 Mm 170 Mm
Test Temperature — 900*C (1652'F)
Alloy Maximum Penetration Average Penetration
CMSX-11B 220 Mm 150 Mm
IN 738 LC 190 Mm
Additional laboratory furnace, crucible type, artificial ash hot corrosion tests were performed. The results of these tests, undertaken at 732'C (1350'F) and 899'C (1650'F), are illustrated
in Figures 2 and 3, respectively. In these tests, the specimens were coated with 1 mg./cm2 Na2S04 every 100 cycles and were cycled 3 times per day. The test at 732 *C was run to about 2400 hours while the one at 899 *C was taken to about 1800 hours.
Further hot corrosion tests were performed with the CMSX-11B alloy. In contrast to the aforementioned tests, the hot corrosion evaluations subsequently undertaken were performed in burner rigs, which is usually a preferred method of testing since the results achieved in burner rig tests generally give more representative indications of the way materials will perform in a gas turbine engine.
The burner rig tests were performed at 900 *C (1652*F) and 1050*C (1922*F), and the test results are reported below in Tables 10 and 11, respectively. The 9 mm diameter x 100 mm long test pins utilized were mounted in a rotating cylindrical jig and exposed to a high speed gas stream. Other test conditions are specified in the respective Tables.
TABLE 10
(Table Removed)
TABLE 11 1050'C (1922*F) HOT CORROSION (BURNER RIG.)
Weight Loss In Grams As a Function of Ttae
(Table Removed)
Several alloys were evaluated within the same rig. The results indicate that CMSX-11B alloy provided much better hot corrosion resistance than IN 738 LC alloy at the 900*C (1652*F) test condition and similar capability at 1050'C (1922T). Furthermore, Figure 4 illustrates that CMSX-11B alloy provides an attractive blend of strength and hot corrosion resistance at 1050'C (1922*F). It is believed that a similar analysis at 900'C would illustrate an even greater blend of capability.
CMSX-11B alloy oxidation tests were performed concurrent to the hot corrosion tests. Table 12 below reports the results of a
laboratory furnace oxidation test performed at 950'C (1742T) for 1000 hour duration. Mean and maximum oxidation depth plus weight gain measurements undertaken at 100 and 500 hour intervals are reported, as well as at test completion.
TABLE 12

(Table Removed)
Figure 5 illustrates the results of 1000'C (1832T) oxidation tests run to as long as 3000 hours. The tests which were performed in an air atmosphere, and measured test specimen weight change as a function of time. The test temperature was cycled to room temperature on a once-per-hour basis. The test results
indicate that the CMSX-llB alloy provides much better oxidation resistance than IN 738 LC, an alloy which is widely used throughout the industrial turbine industry.
Further oxidation test results are illustrated in Figure 6. In this particular test, the pins were cycled to room temperature 3 times per day from the 1010*C (1850'F) test temperature and weight change measured as a function of time. The test was run to about 2400 hours and the results indicate that the CMSX-llB material provides much better oxidation resistance than the alloy IN 738.
Burner rig oxidation testing was undertaken at 1200*C (2192*F), with the results presented in Table 13 below. Various alloys were tested within the same rotating carousel and specimen weight loss was measured at intervals of 100, 200, 300, 400 and 500 hours. Additional test conditions are provided in the Table.
TABLE 13 1200*C (2192*F) OXIDATION (BURNER RIG.)
Weight Less In Graas As a Fine tier ef time

(Table Removed)The burner rig oxidation test results illustrate that the CMSX-11B material provides extremely good 1200'C (2192*F) oxidation resistance in comparison to widely used industrial turbine blade
and vane materials.
An alloy strength and 1200*C (2192*F) oxidation comparison is illustrated in Figure 7. This Figure illustrates that the CMSX-11B alloy blended capability is superior to directional solidified alloys such as Rene 80 H, FSX 414, IN 939 and IN 738 LC alloys.
Additional small VIM heats of the CMSX-11B alloy were produced subsequent to the aforementioned tests. The aim compositions for the CMSX-11B1 and CMSX-11B" materials are reported in Table 1 above. These compositions were produced in order to explore the effects of small changes in the CMSX-11B alloy design. The chemistries achieved for the 270 Ib. (122 kg.) heats produced are reported in Table 2 above, and identified with the respective heat numbers of VG 92 and VG 109. Quantities of these respective heats were investment cast to manufacture single crystal test bars. A chemistry check of the resulting bars indicated that adequate chemistry attainment was realized. Respective single cr tal grain and orientation yields were 100% satisfactory, as experienced with the earlier alloy iterations.
Heat treatment trials led to the selection of a peak solution temperature of 1264"C (2307'F) for both alloys, as reported in Table 3 above. This resulted in solution levels of 99.5 - 100%. Aging treatments were applied as developed for CMSX-11B alloy.
Specimens were prepared for creep-rupture testing, and tests were undertaken at temperature ranging 760 - 1038'C (1400'F - 1900'F). These test results are reported in Table 7 above, and appear to be improved relative to the CMSX-11B experience.
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 true spirit and scope of the present information.

WE CLAIM ;-
1. A process for manufacturing a hot corrosion resistant nickel-based superalloy composition comprising mixing and melting the following elements in percent by weight:
Chromium about 11.5-13.5
Cobalt about 5.5-8.5
Molybdenum about 0.40-0.55
Tungsten about 4.5-5.5
Tantalum about 4.5-5.8
Columbium about 0.05-0.25
Aluminum about 3.4-3.8
Titanium about 4.0-4.4
Hafnium about 0.01-0.06
Nickel + Incidental balance
Impurities
Carbon about 0-0.05
Boron about 0-0.03
Zirconium about 0-0.03
Rhenium about 0-0.25
Silicon about 0-0.10
Manganese about 0-0.10
and cooling to obtain said superalloy composition having a phasial stability number Ny^g less than about 2.45.
2 . A process for manufacturing a superalloy composition as claimed in claim 1, wherein the sum of columbium plus hafnium is from 0.06 to 0.31 percent by weight.
3. A process for manufacturing a superalloy composition as
claimed in claim 1, wherein the Ti:Al ratio is greater than 1.
4. A process for manufacturing a superalloy composition as
claimed in claim 1, wherein the sum of aluminum plus titanium is
from 7.4 to 8.2 percent by weight.
5. A process for manufacturing a superalloy composition as
claimed in claim 1, wherein the Ta:W ratio is greater than 1.
6. A process for manufacturing a superalloy composition as
claimed in claim 1, wherein the said superalloy composition has
an increased resistance to oxidation.
7 - A process for manufacturing a hot corrosion resistant nickel-based superalloy composition, substantially as hereinbefore described with reference to the accompanying drawings.

Documents:

593-del-1995-abstract.pdf

593-del-1995-claims.pdf

593-del-1995-correspondence-others.pdf

593-del-1995-correspondence-po.pdf

593-del-1995-description (complete).pdf

593-del-1995-drawings.pdf

593-del-1995-form-1.pdf

593-del-1995-form-13.pdf

593-del-1995-form-2.pdf

593-del-1995-form-3.pdf

593-del-1995-form-4.pdf

593-del-1995-form-6.pdf

593-del-1995-form-9.pdf

593-del-1995-gpa.pdf

593-del-1995-petition-others.pdf

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Patent Number

190739

Indian Patent Application Number

593/DEL/1995

PG Journal Number

14/2010

Publication Date

02-Apr-2010

Grant Date

16-Aug-2004

Date of Filing

30-Mar-1995

Name of Patentee

CANNON-MUSKEGON CORPORATION

Applicant Address

2875, LINCOLN STREET, MUSKEGON, MI 49441, U.S.A

Inventors:

#	Inventor's Name	Inventor's Address
1	GARY L. ERICKSON	874 WEST STREET, MUSKEGON, MI 49442, U.S.A

PCT International Classification Number

C22C 19/3

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	08/237,510	1994-05-03	U.S.A.