Nickel base superalloys and turbine components fabricated therefrom

Abstract

A nickel base superalloy suitable for the production of a large, crack-free nickel-base superalloy gas turbine bucket suitable for use in a large land-based utility gas turbine engine, comprising, by weight percents:

Description

[0001] The present invention relates to directionally solidified nickel-base superalloys alloys having improved heat treat characteristics, good high temperature longitudinal and transverse creep strength properties, good hot corrosion resistance and resistance to oxidation. The invention also relates to the use of the alloys in the fabrication of turbine components, particularly large turbine buckets and turbine blades for aircraft engines.

BACKGROUND OF THE INVENTION

[0002] It is known to employ nickel base superalloys in the fabrication of aircraft engine components. To be acceptable, such alloys must exhibit good castability with no heat treat cracking, good high temperature longitudinal and transverse creep strength properties and good hot corrosion resistance.

[0003] One such nickel base superalloy employed as a turbine blading material in aircraft engines is single crystal (SC) Rene N4 alloy. A form of SC Rene N4 is described in U.S. Pat. No. 5,154,884 as a nickel-base superalloy composition comprising, by weight, 7-12% Cr, 1-5% Mo, 3-5% Ti, 3-5% Al, 5-15% Co, 3-12% W, up to 10% Re, 2-6% Ta, up to 2% Cb, up to 3% V, up to 2% Hf, the balance being essentially nickel and incidental impurities. U.S. Pat. No. 5,399,313 describes a modified version of SC Rene N4 as comprising, by weight, 9.5-10.0 Cr, 7.0-8.0 Co, 1.3-1.7 Mo, 5.75-6.25 W, 4.6-5.0 Ta, 3.4-3.6 Ti, 4.1-4.3 Al, 0.4-0.6 Cb, 0.1-0.2 Hf, 0.05-0.07 C and 0.003-0.005 B, the balance being nickel and incidental impurities.

[0004] Typically, aircraft engine blades are small, on the order of a few inches long, and weigh a few ounces, or a few pounds at most. Power turbine buckets, by contrast, are typically up to about 36 inches long, and weigh up to about 40 pounds. It has been found that use of single crystal alloys for such large parts is impractical. A need exists for a superalloy for use in the fabrication of large turbine blades which exhibits good castability with no heat treat cracking, good high temperature longitudinal and transverse creep strength properties and good hot corrosion resistance. The present invention seeks to satisfy that need.

SUMMARY OF THE INVENTION

[0005] The present invention is directed to an alloy and high temperature heat treatment for buckets fabricated from nickel base superalloys that will allow the buckets to be used for extended periods, typically up to about 72,000 hours in a power turbine. It is has been found that such an extended turbine life can be achieved if approximately 60-80% solutioning of the gamma-prime precipitates in the alloy occurs. The gamma-prime precipitates provide the strengthening phase for the alloy. Moreover, it has been discovered according to the invention that adjusting the level of boron in the alloy of the invention to within the range of about 70-130 ppm, generally about 80-130 ppm, more usually about 80-100 ppm (about 0.0080-0.01 weight %), for example about 90 ppm (about 0.009 weight %), results in a reduction in the incidence of heat treat cracking in the cast buckets.

[0006] In a first aspect, there is provided a nickel base superalloy suitable for the production of a large, sound, crack-free nickel-base superalloy gas turbine bucket suitable for use in a large land-based utility gas turbine engine, comprising or consisting essentially of, by weight percents:

[0007] Chromium 7.0 to 12.0

[0008] Cobalt 5.0 to 15.0

[0009] Carbon 0.06 to 0.10

[0010] Titanium 3.0 to 5.0

[0011] Aluminum 3.0 to 5.0

[0012] Tungsten 3.0 to 12.0

[0013] Molybdenum 1.0 to 5.0

[0014] Boron 0.0080 to 0.013

[0015] Rhenium 0 to 10.0

[0016] Tantalum 2.0 to 6.0

[0017] Columbium 0 to 2.0

[0018] Vanadium 0 to 3.0

[0019] Hafnium 0 to 2.0 and

[0020] Remainder nickel and incidental impurities.

[0021] A typical nickel base alloy of the invention comprises or consists essentially of, in weight percent:

[0022] Chromium 9.50-10.00

[0023] Cobalt 7.00-8.00

[0024] Aluminum 4.10-4.30

[0025] Titanium 3.35-3.65

[0026] Tungsten 5.75-6.25

[0027] Molybdenum 1.30-1.70

[0028] Tantalum 4.60-5.00

[0029] Carbon 0.06-0.10

[0030] Zirconium 0.01 max (no min)

[0031] Boron 0.008-0.010 (also expressed as 80-100 parts per million (ppm))

[0032] Iron 0.20 max (no min)

[0033] Silicon 0.20 max (no min)

[0034] Manganese 0.01 max (no min)

[0035] Copper 0.10 max (no min)

[0036] Phosphorus 0.005 max (no min)

[0037] Sulfur 0.003 max (no min)

[0038] Columbium 0.40-0.60

[0039] Oxygen 0.002 max (no min)

[0040] Nitrogen 0.0015 max (no min)

[0041] Vanadium 0.10 max (no min)

[0042] Hafnium 0.10-0.20

[0043] Platinum 0.15 max (no min)

[0044] Rhenium 0.10 max (no min)

[0045] Rhenium+Tungsten 6.25 max (no min)

[0046] Magnesium 0.0035 max (no min)

[0047] Palladium 0.10 max (no min)

[0048] Nickel Remainder

[0049] In a further aspect, there is provided a method of making a cast and heat treated article such as a large power turbine bucket of a nickel-base superalloy of the invention, wherein the article is heated in an argon atmosphere or in vacuum to develop 60-80 percent solutioning of gamma prime precipitate, followed by cooling to room temperature. Typically, the article is heated to a temperature of about 2260° F.-2300° F., but at least about 25° F. below the incipient melting temperature of the superalloy. The article may be cooled by a furnace cool at a cooling rate of about 35° F./minute to 2050° F., followed by gas fan cooling at nominally 100° F./minute to 1200° F., and then any cooling rate to room temperature.

[0050] In yet a further aspect, the invention provides an article, such as a large turbine bucket, produced according to the method of the invention.

[0051] In a further aspect, there is provided a gas turbine engine containing an article of the present invention.

[0052] The alloy of the invention exhibits several advantages. First, at 90-130 ppm boron the alloy of the invention has better castability (for large turbine buckets) than SC Rene N4 at 30-50 ppm boron. Secondly, at 90-130 ppm boron in DS form the alloy of the invention has an improved yield over SC Rene N4 at 30-50 ppm boron. In regard to “yield”, SC Rene N4 implies one grain per part. SC Rene N4 is typically used to make small turbine blades. As small parts go, it is possible to have a true “single crystal.” However, for large components, it is difficult to actually produce a part with only one grain. Thus, “yield” for a SC part would be near zero (i.e. it is not possible to fabricate any). By changing the composition of SC Rene N4 primarily by adding more boron, it is possible to make a multi-grained DS component. This multi-grained DS component is designed to accommodate many grains across the cross-section of the part. Made in this manner, the “yield” increases to 80-100%.

[0053] Thirdly, at 90-130 ppm boron, the alloy of the invention has nominally equivalent mechanical properties (in the longitudinal direction) to the SC Rene N4 at 30-50 ppm boron. Fourthly, at 90-130 ppm boron, the alloy of the invention has better transverse creep properties than SC Rene N4 at 30-50 ppm. Fifthly, at 90 ppm boron, the alloy of the invention has better resistance against heat treat cracking than either the SC Rene N4 at 30-50 ppm boron or the 130 ppm boron DS alloy of the invention. The alloy with 130 ppm boron has a lower melting point (approx. 2301° F.) than DS Rene N4 or DS Rene N4 with 90 ppm boron (m.p. approx. 2315° F.), or SC Rene N4 which has a melting point near 2334° F. (Melting points: DS Rene N4 with 130 ppm boron—2301° F.; DS Rene N4 with 90 ppm boron—2315° F.; SC Rene N4 with 30-50 ppm boron—2334° F.).

BRIEF DESCRIPTION OF THE DRAWINGS

[0054] The invention will now be described in more detail with reference to the accompanying drawings, in which:

[0055] FIG. 1 is a series of plots showing the effect of different processing conditions on crack length in a MS7001 H turbine bucket; and

[0056] FIG. 2 is a regression plot showing creep strength as a function of temperature;

[0057] FIG. 3 is a regression plot showing transverse creep strength (%) as a function of boron content (ppm);

[0058] FIG. 4 is plot showing creep elongation as a function of test temperature;

[0059] FIG. 5 is a plot showing the effect of varying amounts of boron on incipient melting of SC or DS Rene D4;

[0060] FIG. 6 shows a third and fourth stage bucket fabricated from an alloy of the invention; and

[0061] FIG. 7 is a gas turbine engine showing the location where buckets of the invention are used.

DETAILED DESCRIPTION OF THE INVENTION

[0062] It has been found, according to the invention, that increasing the boron from about 30-50 ppm in the SC Rene N4 specification to no greater than 130 ppm boron, along with several changes in part configuration, including bucket shape, essentially eliminates casting cracks in large turbine buckets. The additional boron may create a “M5B3” phase where M is Ni or Ni5B3 eutectic phase in the grain boundaries and elsewhere within the alloy matrix (as determined by Auger Spectrometry and Microdiffraction analyses), and the melting properties of the alloy have been attributed to the presence of a “M5B3” boron phase. The presence of this eutectic phase lowers the incipient melting point (the point at which the metal starts to melt) from 2334° F. to 2301° F. (as determined by Differential Thermal Analysis (DTA)). Thus, after application of a 2320° F. heat treatment (normal for SC Rene N4), the DS alloys begin to melt at locations within the eutectic pools where the boron as Ni5B3 is concentrated. Many of these eutectic pools are in the grain boundaries, and can be more segregated than those eutectic pools elsewhere within the grains. When the eutectic melting starts and the bucket cools back down to room temperature, a linear imperfection defined as a crack may be created. These cracks, called heat treat cracks, may be several inches long but may not be visible to the unaided eye. The heat treat cracks may be found by use of fluorescent penetrant inspection (FPI), a nondestructive inspection technique.

[0063] The inventors have carried out work to determine parameters with respect to the boron content of the alloy. It has been found that boron at 30-50 ppm in the alloy of the invention is not particularly suitable for castability of large buckets. At this level of boron, a 2320° F. heat treatment fully solutions the gamma-prime phase and provides optimum longitudinal mechanical properties for long bucket life. However, at this low level of boron, the transverse creep properties are less than optimum for large buckets.

[0064] In contrast, boron at 130 ppm in the alloy has been found to be suitable for castability, but is not particularly suitable for a full solution heat treatment. The melting point of such an alloy is reduced to about 2301° F., and the highest heat treatment that may be reliably applied is 2280° F. if melting is to be avoided. Heat treatment at a temperature of 2280° F. provides only about 60-80% solutioning of the gamma-prime phase, but this is generally acceptable for a full-life bucket. Thus, the gamma-prime phase in the 130 ppm boron material cannot be fully solutioned because the alloy starts to melt before full solutioning can be achieved.

[0065] The transverse creep properties are acceptable with this higher level of boron of 130 ppm. However, at this level of boron, a 5% failure rate for heat treat cracking has been observed.

[0066] It has been found that a level of boron of about 80-100 ppm, i.e. about 90±10 ppm, is optimum for castability. In order to improve the longitudinal creep properties for an improved margin for bucket life, an increase in the percent gamma-prime solutioning over about 60-80% is desired. This may be possible due to the increase in melting temperature for the intermediate (about 90 ppm) boron level. In addition, this 90 ppm level of boron provides a greater margin against heat treat cracking, and increases the yield during the solution heat treatment operation.

[0067] Castability experiments have been performed using the procedure described in U.S. Pat. No. 4,169,742 (herein incorporated by reference). A master “lean” heat of DSN4 was formed, where B and Zr were removed, but otherwise the remaining elements (except for C and Hf) were the same as in SC Rene N4 as described above. A three-level, four-factor designed experiment (DOE) was then carried out. Castability was examined using the aforementioned castability test with the grain boundary strengthening elements (& Ti) at the following levels (Zr was not varied but kept at the lowest level), as shown in the Table below: 1 Weight Percent of Elements at the 3 levels Desired for DOE Experiment Element Low Level Medium Level High Level Carbon 0.06 0.10 0.14 Hafnium 0.25 0.45 0.65 Boron 0.0075 (75 ppm) 0.01 (100 ppm) 0.015 (150 ppm) Titanium 3.37 3.50 3.65

[0068] It has been determined that castability is improved if Hf and Ti are run at their highest levels, but this also depends upon the B content. The differences between C and B could not be fully ascertained because this was not a full factorial experiment (which would have been 3×3×3×1×3 or 81 experiments), and due to the limited ranges of carbon (0.14%−0.06%=0.08%) and boron (0.015%−0.0075%=0.0075%) versus ranges for hafnium (0.65%−0.25%=0.45%) and titanium (3.65%−3.37%=0.28%).

[0069] Hafnium (Hf) is known to cause casting defects known as “bands”, which are transverse linear indications as determined during FPI examination. It has been determined that 0.75% Hf causes bands in low or high boron DS Rene N4 (boron 30-50 ppm—or 80-130 ppm), whereas 0.25 weight % Hf and 0.45 weight % Hf resulted in no bands. From the standpoint of acceptable transverse creep ductility, the lower level of Hf in production buckets is not allowed to fall below 0.15 weight %. Thus, for DS Rene N4, Hf is generally maintained in the range of about 0.15-0.45 weight %.

[0070] Experiments have been carried out using controlled amounts of boron and hafnium added to a baseline N4 master heat to determine their effect on castability, expressed as total inches of crack length. The master heat composition was, by weight, 0.04%C, 9.77% Cr, 7.49% Co, 5.92% W, 1.51% Mo, 4.21% Al, 3.37% Ti, 0.45% Nb, 4.71% Ta, 0.16% Hf, 0.00% B, less than 0.005% Zr, balance Ni. The results for thin wall castings (about 60 mils thick) and thick wall castings (about 120 mils thick) are shown in the chart below. The least amount of cracking (expressed as inches of crack) is best. 2 “Inches of Crack Length from Castability Test” 1 2 3 Other heats made by doping master lean heat

[0071] The chart above shows that thin wall versus thick wall data are comparable, and that best castability is observed for DS Rene N4 with 40 ppm (0.004%) boron and no Hf, OR 130 ppm (0.013%) boron and 0.45% Hf, indicating there is a “saddle point” in the data. No Hf is not considered to be acceptable as it may decrease transverse creep ductility. It has been found that castability of the 90 ppm boron alloy with 0.15% Hf is improved over the castability of 130 ppm boron material with 0.15% Hf. Higher Hf levels may create transverse “bands” or dross. Banding as noted earlier is a known casting flaw, and “dross” is a nonmetallic inclusion caused by a chemical reaction between dissolved oxygen in the metal and free hafnium in the metal which combine to form a stable oxide such as HfO2 (hafnium oxide). In either case, lower Hf (typically 0.15-0.45 weight %) is desirable in creating defect-free castings.

[0072] The method of the invention includes a ramp heat treatment up to the solution heat treatment temperature plus the post-solution heat treatment cooling rate down to room temperature. Four factors are important to achieving reduced heat treatment cracking. Each has been investigated at two levels, as discussed below.

[0073] HIP temperature (2175° F. or 2225° F.);

[0074] solution heat treat temperature (2270° F. or 2290° F.);

[0075] post-solution heat treatment temperature cooling rate (slow furnace cool at about 35° F./minute, or fast gas fan cool at about 150° F./minute, both followed by gas fan cooling from a temperature of about 2050° F.); and

[0076] solution heat treatment atmosphere (vacuum or argon gas).

[0077] HIP or “hot isostatic pressing” is a means by which internal porosity in the casting can be closed by the application of external pressure. This is achieved in a HIP vessel. The porosity is closed by the application of temperatures in the range of 2175° F.-2225° F. and 15,000 psi for an alloy like SC or DS Rene N4.

[0078] A heat treat temperature of 2290° F. was chosen as the highest temperature possible for the solution heat treatment. The temperature of 2290° F. was reached using part of a RAMP4 cycle to 2290° F., which is set forth in the Table which follows: 3 Typical RAMP4 Solution Heat Treatment Cycle to 2300 F. Hold Heating Ramp Rate Temp. Hold Time Rate Purpose/Results 25 F./minute 1400 F.  10 mm. — Stabilize, and begin introducing 800 microns of argon gas. Not used if already running in a 100% argon atmosphere. 25 F./minute 2225 F.   8 hour Increase to homogenize 25 F./hour 2250 F.   4 hours Increase to homogenize 30 F./hour 2280 F.   2 hours Increase to homogenize 10 F./hour 2290 F.   2 hours Increase to homogenize 10 F./hour 2300 F. 0.5 hours Cool to RT Achieve final gamma-prime solutioning

[0079] This heating cycle was chosen because there was no evidence of melting or heat treat cracking using a variety of bucket or ingot sizes. For the 2290° F. solution cycle, that part of the RAMP4 cycle above (including up to 2290° F./2 hours) was chosen. A temperature of 2290° F. was chosen because previous work by the inventor showed that at 2300° F., recrystallized grain (RX) defects could form in DS Rene N4, and to avoid the RX grains the temperature would have to be lowered. Since it is only possible to control the temperature to within 10° F., a temperature of 2290° F. was chosen as the highest practical heat treatment temperature.

[0080] The second solution heat treatment temperature was 2270° F. This was based upon metallography photographs showing the percent of gamma-prime solutioning, and was considered to be the lowest acceptable temperature capable of providing a full-life bucket.

[0081] The results are set forth in FIG. 1. Heat treating at 2270° F.±10° F. was equivalent to heat treating in the range of 2260-2280° F., and heat treating at 2290F±10° F. was equivalent to heat treating in the range of 2280-2300° F.

[0082] A reason that it is difficult to determine what causes heat treat cracking is because the buckets cannot be examined at the solution heat treatment temperature to see if they are cracked. It is necessary to cool the buckets down to room temperature for examination. In addition, the section size of the bucket has some effect on residual stress, which further complicates the heat treat cracking issue.

[0083] The HIP temperature was probably not significant because it is well below the incipient melting temperature. Furthermore, the HIP cycle is also a thermal cycle and therefore can provide some homogenization to the DS Rene N4. In this case, the 2225° F. cycle would provide more homogenization than the 2175° F. cycle. But based upon the experimental analysis, it was shown the amount of homogenization provided by either HIP cycle is inadequate to influence the heat treat cracking.

[0084] In addition to the previous HIP and solution heat treat cycles, the cooling rate was believed to have an effect on heat treat cracking. To investigate this, two cooling rates were employed. The first rate was produced from a gas fan cool in the range of 100-150° F./minute, which is available on most vacuum furnaces. The second rate was selected because it was used during development trials, specifically from Ramp 4 heat treatment where gas fan cooling was not available—only natural cooling was available (called furnace cooling). Furnace cooling is achieved by just turning off the furnace and letting it cool naturally. In this case, the range was measured to be 35-75° F./minute.

[0085] Finally, the furnace atmosphere was felt to be important. Two atmospheres are commonly available. The first is a vacuum atmosphere with some argon backfill, in the range of 400-800 microns. The second atmosphere that is commonly employed (and was used in RAMP 4 heat treat) was 100% argon (not a vacuum).

[0086] The furnace environment during the heat treat experiment was determined to be a minor factor. Initially, it was thought a vacuum or partial vacuum environment could cause heat treat cracking by volatilizing the grain boundary elements. In this instance, during a vacuum heat treatment, some elements with a low vapor pressure can be removed from the alloy, possibly leaving void spaces such as along a grain boundary (which could be interpreted as a crack). However, neither atmosphere (vacuum with partial pressure argon or 100% argon) had a significant effect on the heat treat cracking of the DS Rene N4 buckets.

[0087] FIG. 1 shows that the cooling rate has the greatest influence on the heat treat cracking, followed closely by the solution heat treatment temperature (the greater the slope, the larger the effect). The other two factors—HIP temperature and furnace atmosphere—are considered to be minor factors. Thus, the slower cooling rate and the lower solution heat treatment temperature afforded the best results (least amount of heat treat cracking).

[0088] When the alloy is DS Rene N4 alloy with 130 ppm boron, the optimum heat treatment includes a HIP cycle at 15,000 psi for 4 hours in the range of 2175-2225° F. followed by a solution heat treatment temperature in the range of 2270° F. to 2290° F., followed by a furnace cool of about 35° F./minute to about 2050° F. and gas fan cooling to less than 1200° F., to prevent heat treat cracking.

[0089] The solution temperature had the largest effect on heat treat cracking, and is generally 2280° F.±10° F. (i.e. 2270° F.-2290° F.), more usually 2280° F. This provides for a lower incidence of heat treat cracking while still achieving adequate gamma-prime precipitate solutioning.

[0090] The cooling rate is generally in the range of 25-45° F./minute, for example 35° F./minute. The gas fan cooling may be initiated when the temperature reaches approximately 2050° F.±50° F.

[0091] The furnace atmosphere may be 100% argon, or vacuum plus argon partial pressure (400-800 microns). Vacuum plus argon partial pressure (400-800 microns) is generally employed. The use of this small amount of argon helps reduce the vaporization (depletion) of chromium during the heat treat cycle.

[0092] From this 130 ppm boron group, 1 cracked bucket occurred out of 19 total, or a 5.2% failure rate, due to heat treat cracking. Part of the reason for this is the small margin of error between the heat treat temperature (2280° F.) and the incipient melting point of this alloy (2301° F.). The temperature difference between heat treat temperature and melting point is 2301−2280° F.=21° F. This small margin is less than the error of thermocouples, which would approach 1% of the actual temperature, or at 2280° F. it would be 22.8° F. This means the actual heat treat temperature could exceed the true melting point of the alloy, without the furnace operator's knowledge. If that happened, it would cause incipient melting, which in the presence of residual stress may lead to heat treatment cracks. This is compared to a margin of 54° F. for the 40 ppm boron material between the heat treat temperature and the potential for incipient melting and heat treat cracking (2334° F.−2280° F.=54° F.)

[0093] The margin for temperature error with a 2280° F. heat treatment is shown in the Table below. 4 Incipient Aim Heat Melting Point Treat Margin for Temp. DSN4/GTD444 (° F., on Temperature Error during Heat Alloys heating) (° F.) Treatment (° F.) DSN4 w/31 ppm 2346 2280 66 Boron DSN4 w/36 ppm 2344 2280 64 Boron DSN4 w/40 ppm 2334 2280 54 Boron DSN4 w/90 ppm 2311 2280 31 Boron DSN4 w/130 ppm 2301 2280 21 Boron

[0094] The advantage in going to an intermediate level of boron, such as in the 80-100 ppm range, is in the margin between incipient melting (when the alloy starts to melt) at the 2280F heat treat temperature. For example, at 130 ppm B, there is only 21° F. between the incipient melting point and the 2280° F. heat treatment. This is not an acceptable range, because the error due to the thermocouple (TC) alone is 22.8F (1% of 2280F). But at 90 ppm B the range between incipient melting and the heat treat temperature has increased to 31° F. Therefore, after accounting for 22.8° F. of TC error, there is still 8.2° F. of temperature margin (31° F.−22.8° F.) between the incipient melting point and the 2280° F. heat treat temperature. While 8.2° F. of margin is not a lot, it is an equivalent margin when compared to other high-technology SC or DS alloys.

[0095] Buckets from 90 ppm boron heats were successfully heat treated at 2280° F. with 0% failure rate due to heat treat cracking. For the 90 ppm boron material, the melting point was determined to be 2311° F. Thus, with a heat treat temperature of 2280° F. the temperature difference between the heat treat temperature and the melting point is 2311−2280° F.=31° F. The temperature difference between the heat treat temperature and the incipient melting point is greater than the thermocouple error (1% of 2280° F. or 22.8° F.), so there is less opportunity for unknowingly heat treating the buckets above their incipient melting point, causing heat treat cracking.

[0096] It has been found that the amount of boron influences the incipient melting point of the alloy, i.e. less boron is better. The amount of boron additionally influences the transverse creep ductility, i.e. more boron is better (although boron does not influence the longitudinal creep ductility). Moreover, a higher solution temperature leads to more gamma prime solutioning, and more gamma prime solutioning leads to more longitudinal creep life. However, the solution temperature influences the transverse creep ductility, whereby a lower temperature is better.

[0097] Thus, optimization of the alloy requires transfer functions (equations) that describe these features in terms of controllable factors. Additionally, creep strength and casting yield are not measured in similar units. Therefore, the transfer function is expressed as a percentage of the best case for heat treat yield (100%) and creep strength (100%). The transfer function generation is described below.

[0098] Heat treat yield is a function of two variables, boron content and solution heat treatment temperature. If the B content is too high, incipient melting or heat treat cracking occurs at segregated areas in the casting, resulting in scrap. If the solution heat treatment temperature is too high, incipient melting and recrystallization (RX) limit yield. Recrystallized grains result from a phase transformation where residual strains in the material on heating cause the formation of strain-free grains with little or no strength, i.e. critical defects. The following spreadsheet shows the data used to generate Heat Treat Yield Transfer Function Equation 1: 5 Heat Treat Yield Boron (B) (Percent) Temp. (F.) Content (ppm) 100 2280 40 50 2292 130 50 2310 40 90 2280 130 0 2327 40 0 2310 130

[0099] Regression with the data leads to the following regression equation:

Heat Teat Yield=5448−2.34(Temp)−(0.340)*(Boron content)  Eq. 1

[0100] This is the first transfer function for yield.

[0101] A statistical analysis was conducted for the data, resulting in the following standard tables: 6 Predictor Coef StDev T P VIF Constant 5448.0 671.8 8.11 0.004 Temp −2.3353 0.2907 −8.03 0.004 1.1 B −0.3398 0.1117 −3.04 0.056 1.1

[0102] S=11.59 R-Sq.=95.6% R-Sq. (Adj)=92.6%

[0103] (R-Sq=R2 or R squared; adj means Adjusted)

[0104] The next transfer function is for longitudinal creep strength. This is a function of gamma-prime precipitate solutioning versus the solution heat treatment temperature, as the only way to get 100% creep strength is to fully solution the material. The following is data relating the percent of full creep strength versus the heat treat temperature for DS Rene N4: 7 Creep Heat Treat Strength Temperature (Percent) (F.) 100 2320 90 2300 60 2280 40 2215

[0105] The longitudinal creep strength is in percent of maximum obtainable, and the heat treatment temperature (t) is the solution heat treatment temperature in degrees F.

[0106] The data was used to solve for Equation 2 (see the Regression Plot in FIG. 2). The curve has the correct dependency of creep strength on solution heat treatment temperature. It will be noted that as-cast DS Rene N4 has about 40% of the possible creep strength and that solution heat treatment of DS Rene N4 at 2320° F. gives 100% creep strength. This is the second transfer function.

[0107] A further important feature of the alloy is creep strength transverse (transverse creep strength) to the grain boundaries. This is important in the tip shroud and other areas where loading is not in a radial direction on he part. The following data was extracted for transverse creep strength: 8 Percent of Transverse Creep Boron Content Strength. (ppm) 50 40 100 80 80 130 90 100

[0108] This information created a non-linear regression plot as shown in FIG. 3. Equation 3 is:

Y=−40.7431+2.9113X−1.54E−02X2

[0109] The three transfer functions (equations) can be solved simultaneously using an optimization spreadsheet shown below: 9 MULTIPLE RESPONSE OPTIMIZATION 4 5 6 7

[0110] The solutions with respect to Heat Treat Yield, Longitudinal Creep and Transverse Creep Strength were: 10 Needs Heat Treat Yield 1 1 2 2 3 3 Longitudinal Creep Strength 2 3 1 3 1 2 Transverse Creep Strength 3 2 3 1 2 1 Optimize B ppm 40 40 94.5 94.5 40 94.5 Temp F 2280 2280 2296 2280 2296 2280

[0111] A “1” means optimization on this need first, followed by “2” and finally “3”.

[0112] This results in an optimized alloy with a boron content of 94.5+/−10 ppm and a heat treatment temperature of 2280±20° F.

[0113] FIG. 4 is plot showing creep elongation as a function of test temperature. FIG. 5 is a plot showing the effect of varying amounts of boron on incipient melting of SC or DS Rene N4.

[0114] FIG. 6 shows a third and fourth stage bucket fabricated from an alloy of the invention. FIG. 7 is a gas turbine engine showing the location where buckets of the invention are used.

[0115] While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A nickel base superalloy suitable for the production of a large, crack-free nickel-base superalloy gas turbine bucket suitable for use in a large land-based utility gas turbine engine, comprising, by weight percents:

Chromium 7.0 to 12.0

Carbon 0.06 to 0.10

Cobalt 5.0 to 15.0

Titanium 3.0 to 5.0

Aluminum 3.0 to 5.0

Tungsten 3.0 to 12.0

Molybdenum 1.0 to 5.0

Boron 0.0080 to 0.0130

Rhenium 0 to 10.0

Tantalum 2.0 to 6.0

Columbium 0 to 2.0

Vanadium 0 to 3.0

Hafnium 0 to 2.0 and

remainder nickel and incidental impurities.

2. The nickel base superalloy according to claim 1, wherein boron is present in an amount of about 0.008-0.010 weight percent.

3. The nickel base superalloy according to claim 1, wherein boron is present in an amount of about 0.009 weight percent.

4. The nickel base superalloy according to claim 1, wherein hafnium is present in an amount of about 0.015-0.45 weight percent.

5. A nickel base superalloy suitable for the production of a large, crack-free nickel-base superalloy gas turbine bucket suitable for use in a large land-based utility gas turbine engine, comprising, by weight percents

Chromium 9.50-10.00

Cobalt 7.00-8.00

Aluminum 4.10-4.30

Titanium 3.35-3.65

Tungsten 5.75-6.25

Molybdenum 1.30-1.70

Tantalum 4.60-5.00

Carbon 0.06-0.10

Zirconium 0.01 max

Boron 0.008-0.010

Iron 0.20 max

Silicon 0.20 max

Manganese 0.01 max

Copper 0.10 max

Phosphorus 0.005 max

Sulfur 0.003 max

Columbium 0.40-0.60

Oxygen 0.002 max

Nitrogen 0.0015 max

Vanadium 0.10 max

Hafnium 0.10-0.20

Platinum 0.15 max

Rhenium 0.10 max

Rhenium+Tungsten 6.25 max

Magnesium 0.0035 max

Palladium 0.10 max

Nickel Remainder

6. A method of making a cast and heat treated article of a nickel-base superalloy, comprising the steps of:

(a) providing a superalloy of the composition of claim 1;

(b) heating the superalloy to develop at least 60 percent solutioning of gamma prime precipitate; and

(c) cooling to room temperature.

7. The method according to claim 6 wherein the article is heated to a temperature of about 2260° F.-2300° F. but at least about 25° F. below the incipient melting temperature of the superalloy.

8. The method according to claim 6 wherein the article is cooled by a furnace cool at a rate of about 35° F./minute to about 2050° F.

9. The method of claim 6 wherein the wherein the article is cooled by a gas fan cool at a rate of about 100-150° F./minute from below about 2050° F.

10. The method of claim 6, wherein said heating is carried out in an argon atmosphere.

11. The method of claim 6 wherein said heat treating comprises the steps of:

(a) heating said article to a temperature of about 1400° F. at a rate of 25° F./minute and holding for about 10 minutes;

(b) heating said article in (a) to a temperature of about 2225° F. at a rate of 25° F./minute and holding for about 8 hours;

(c) heating said article in (b) to a temperature of about 2250° F. at a rate of 25° F./minute and holding for about 4 hours;

(d) heating said article in (c) to a temperature of about 2280° F. at a rate of 30° F./minute and holding for about 2 hours; and

(e) cooling to room temperature.

12. The method according to claim 11 wherein the article is cooled by a furnace cool at a rate of about 35° F./minute to about 2050° F.

13. The method of claim 11 wherein the wherein the article is cooled by a gas fan cool at a rate of about 100-150° F./minute from below about 2050° F.

14. The method of claim 6 wherein said article is a large turbine bucket.

15. The method of claim 6 wherein said article is a large aero engine turbine blade.

16. An article produced by the method of claim 6.

17. An article of claim 16 which is directionally solidified.

18. An article of claim 16 which is conventionally cast.

19. An article of claim 16 which is single crystal cast.

20. A gas turbine engine containing an article of claim 16.