CA1337624C - Nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries - Google Patents
Nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundariesInfo
- Publication number
- CA1337624C CA1337624C CA000516576A CA516576A CA1337624C CA 1337624 C CA1337624 C CA 1337624C CA 000516576 A CA000516576 A CA 000516576A CA 516576 A CA516576 A CA 516576A CA 1337624 C CA1337624 C CA 1337624C
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- nickel
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- grain boundaries
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/52—Alloys
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
There is provided by the present invention nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries and an improved balance between cyclic oxidation and hot corrosion resistance. The improved tolerance arises from the discovery that nickel-base superalloys suitable for casting as single crystal articles can be improved by the addition of small, but controlled, amounts of boron and carbon, and optionally hafnium, and is manifested principally by improved grain boundary strength. As one result of this increased grain boundary strength, grain boundary mismatches far greater than the 6° limit for prior art single crystal superalloys can be tolerated in single crystal articles made from the nickel-base superalloys of this invention. This translates, for example, into lower inspection costs and higher casting yields as grain boundaries over a broader range can be accepted by visual inspection techniques without resort to expensive X-ray techniques. These alloys are especially useful when directionally solidified as hot-section components of aircraft gas turbine engines, particularly rotating blades and stationary vanes.
Description
6~
NICKEL-BASE SUPERALLOYS FOR PRODUCING
SINGLE CRYSTAL ARTICLES HAVING IMPROVED
TOLERANCE TO LOW ANGLE GRAIN BOUNDARIES
CROSS-REFERENCE TO RELATED APPLICATION
The invention disclosed and claimed herein is related to the invention disclosed and claimed in Canadian Application Serial No. 400,748, filed April 8, 1982.
BACKGROUND OF THE INVENTION
This invention pertains generally to nickel-base superalloys castable as single crystal articles of manufacture, which articles are especially useful as hot-section components of aircraft gas turbine engines, particularly rotating blades.
The efficiency of gas turbine engines depends significantly on the operating temperature of the various engine components with increased operating temperatures resulting in increased efficiencies. The search for increased efficiencies has led to the development of heat-resistant nickel-base superalloys which can withstand increasingly high temperatures yet maintain their basic material properties. The requirement for increased operating temperatures has also lead to the development of highly complex cast hollow shapes, e.g., blades and vanes, which provide efficient cooling of the material used to produce such shapes.
The casting processes used with early generations of nickel-base superalloys, commonly . .
~., ^~
referred to as conventionally cast nickel-base superalloys, generally produced parts whose microstructures consisted of a multitude of equiaxed single crystals (grains) of random ~nonoriented) crystallographic orientation with grain boundaries between the grains. Grain boundaries are regions of highly nonoriented structure only a few atomic diameters wide which serve to accommodate the crystallographic orientation difference or mismatch between adjacent grains.
A high angle grain boundary (HAB) is generally regarded as a boundary between adjacent grains whose crystallographic orientation differs by more than about 5-6 degrees. High angle grain boundaries are regions Of high surface energy, i.e., on the order of several hundreds of ergs/cm2, and of such high random misfit that the structure cannot easily be described or modelled. Due to their high energies and randomness, high angle grain boundaries are highly mobile and are preferential sites for such solid-state reactions as diffusion, precipitation and phase transformations;
thus, high angle boundaries play an important role in the deformation and fracture characteristics and chemical characteristics (e.g., resistance to oxidation and hot corrosion) of polycrystalline metals.
Also, due to the high energies and disorder of HABs, impurity atoms are attracted preferentially (segregated) to high angle grain boundaries to the degree that the concentration of impurity atoms at the grain boundary can be several orders of magnitude greater than the concentration of the same impurity atoms within the grains. The presence of such high concentrations of impurity atoms at high angle grain boundaries can further modify the mechanical and chemical properties of metals. ~or example, in 133~24 13~V-8137 nickel-base superalloys, lead and bismuth are deleterious impurities which segregate to the grain boundaries. At high temperatures, even small amounts (i.e., a few ppm) of such impurities in the grain boundaries of nickel-base superalloys degrade the mechanical properties (e.g., stress-rupture strength) and failure generally occurs at the grain boundaries.
In contrast to high angle grain boundaries, low angle grain boundaries, sometimes also called subgrain boundaries, are generally regarded as boundaries between adjacent grains whose crystallographic orientation differs by less than about 5 degrees. It is to be understood, however, that the classification of a boundary as high angle or low angle may vary depending upon the person or organization doing the classification. For the limiting case of a low angle boundary (LAB) where the orientation difference across the boundary may be less than 1 degree, the boundary may be described (modelled) in terms of a regular array of edge dislocations, i.e., a tilt boundary. While the mismatch is technically that between any two adjacent grains, and not that of the boundary per se, the extent of the mismatch is commonly assigned to the boundary; hence the terminology of, for example, a 5 degree low angle boundary, which usages shall be used herein interchangeably.
Low angle grain boundaries are more highly ordered and have lower surface energies than high angle grain boundaries. Higher order and lower energy result in boundaries with low mobility and low attraction for impurity atoms which, in turn, results in a lesser effect on properties, mechanical and chemical, compared to high angle grain boundaries. Thus, while no grain boundaries constitute a preferred condition, low angle boundaries are to be preferred over high angle grain boundaries.
1~37624 13~V-81a7 Improvements in the ability of conventional superalloys to withstand higher temperatures without impairing other needed qualities, such as strength and oxidation resistance, was achieved through alloy development and the introduction of improved processing techniques. These improvements followed fro~ findings that the strength of such superalloys, and other important characteristics, were dependent upon the strengths of the grain boundaries. To enhance such conventional superalloys, initial efforts were aimed at strengthening the grain boundaries by the addition of vario~s grain boundary strengthening elements such as carbon (C), boron ~B), zirconium (Zr), and hafnium (Hf) and by the removal of deleterious impurities such as lead (Pb) or bismuth (Bi) which tended to segregate at and weaken the grain boundaries.
- Efforts to further increase strength levels in conventional nickel-base superalloys by preferentially orienting the grain boundaries parallel to the growth or solidification direction were subse~uently initiated. Preferential orientation of the grains generally results in a columnar grain structure of long, slender (columnar) grains oriented in a single crystallographic direction and minimizes or eliminates grain boundaries transverse to the growth or solidification direction. The process used, i.e., directional solidification (DS), had long been used for other purposes such as the manufacture of magnets and grain-oriented silicon steel for transformers. That process has been described and impro~ed upon, for instance, in U.S. Patent 3,897,815 - Smashey.
-Compared with conventionally cast superalloy articles, directionally solidified (~S'd) articles exhibited increased strength when the columnar grains were aligned parallel to the principal stress axis due to the elimination or minimization of grain boundaries transverse to the direction of solidification. In addition, DS provided an increase in other properties, such as ductility and resistance to low cycle fatigue, due to the preferred grain orientation. ~owever, reduced strength and ductility properties still existed in the transverse directions due to the presence of longitudinal columnar grain boundaries in such DS'd articles. Additions of Hf, C, B, and Zr were utilized to improve the transverse grain boundary strength of such alloys as was done previously in conventional equiaxed nickel-base superalloys. However, large additions of these elements acted as melting point depressants and resulted in limitations in heat treatment which did not allow the development of maximum strengths within such directionally solidified superalloys.
It has been recognized for some time that articles could be cast in various shapes as a perfect single crystal, thus eliminating grain boundaries altogether. A logical step then was to modify the DS
process to enable solidification of superalloy articles as single crystals to eliminate longitudinally extending high angle grain boundaries previously found in DS'd articles.
In the single crystal metallic alloy arts, it has heretofore been conventional teaching that elements such as boron, zirconium, and carbon are to be avoided, i.e., kept to the lowest levels possible with commercial melting and alloying practice and 35 technology. For example, U.S. Patent 3,494,709 recites - 1337~2~
the deleterious effect of B and ~r, proposing limits of O.U01~ and 0.01~ for those elements, respectively.
U.S. Patent 3,567,526 teaches that the fatigue properties of single crystal superalloy articles can be improved by the complete removal of carbon.
In U.S. Patent 4,116,723, there is disclosed homogeneous single crystal nickel-base superalloy articles having no intentional additions of cobalt (Co), B, Zr or C which are said to have superior mechanical properties, e.g., creep and time to rupture, compared to similar nickel-base superalloys containing Co, C, B, and Zr. Therein it is taught that cobalt should be restricted to less than about 0.5~, and more preferably to less than about 0.2~, to preclude the formation of deleterious topologically close packed phases (TCP) (e.g., ~ and ~). Further, it is taught therein that no single element of the group carbon, boron, and zirconium should be present in an amount greater than 50 ppm, that preferably the total of such impurities be less than 100 ppm and, most preferably, that carbon be kept below 30 ppm and that ~ and Zr each be kept below 20 ppm. In any event, it is taught that carbon must be kept below that amount of carbon which will form MC type carbides. Subse~uently, in U.S.
Patent 4,209,348 it was shown that 3-7~ Co could be included in the single crystal nickel-base superalloys disclosed therein without forming TCP.
Another purpose in limiting C, B, and Zr is to increase the incipient melting temperature in relation to the gamma prime solvus temperature thus permitting solutionizing heat treatments to be performed at temperatures where complete solutionizing of the gamma prime phase is possible in reasonable times without causing localized melting of solute-rich regions.
~ecently, however, it has been recognized, U.S. Patent 4,402,772, that the addition of hafnium in small 133762~
13~V-8137 amounts to certain of nickel-base superalloys for the casting of single crystal articles is effective, for example, in providing enhanced properties and enhanced heat treatability in that such articles have a greater s temperature range between the gamma prime solvus and incipient melting temperatures than do most prior art single crystal articles.
SU~ARY OF THE I~VENTION
There is provided by the present invention nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries. The improved tolerance to low angle grain boundaries arises from the discovery that nickel-base superalloys suitable for casting as single crystal articles can, contrary to the teachings of the prior art, be improved by the addition of small, but controlled, amounts of boron and carbon, and optionally hafnium, and is manifested principally by improved grain boundary strength. Additionally, the superalloys of this invention also possess an improved balance between cyclic oxidation and hot corrosion resistance tue primarily to the carbon and hafnium and an increased Al to Ti ratio.
As one result of this increased grain boundary strength, grain boundary mismatches far greater than the 6 limit for prior art single crystal superalloys can be tolerated in single crystal articles made from the nickel-base superalloys of this invention. This translates, for example, into lower inspection costs and higher yields as grain boundaries over a broader range can be accepted by the usual inspection techniques without resorting to expensive X-ray techniques. The superalloys of this invention are especially useful when directionally solidified as hot-section components of aircraft gas turbine engines, particularly rotating blades.
133~624 Broadly, the single-crystal superalloys of this invention consist essentially of about, by weight, 7-12~ Cr, 5-1~ Co, 0.5-5~ Mo, 3-12~ W, 2-6$ Ta, 2-5 Ti, 3-5~ Al, 0-2~ Cb, 0-2.0~ ~f, 0.03-0.25% C and 0.002-0.050% B, the balance being nickel and incidental impurities.
D~lAILED DESCRIPTION OF THE DRAWINGS
FIGURE 1 is a perspective schematic view of a blade member for use in a gas turbine engine;
FIGURE 2 is a perspective schematic view of a directionally solidified slab-like single crystal ingot marked for removal of blanks to be processed into mechanical property test specimens;
FIGURE 3 is a graph of comparative stress-rupture life versus alloy boron content;
FIGURE 4 is a graph of comparative stress-rupture life versus grain boundary misfit; and FIGURE 5 is a graph of external metal loss in cyclic oxidation as a function of exposure time.
DETAILEV DESCRIPTION OF THE INVENTION
Nickel-base superalloys castable as single crystals have typically been used to manufacture airfoil members, e.g., rotating blades and stationary vanes, for the hot section of aircraft gas turbine engines. ~uch a blade member 10 is shown schematically in FI~. 1 and includes base (or root) portion 12 (shown machined to a "fir-tree" configuration for attachment to a disk), platform portion 14, and aerodynamically curved airfoil portion 16. Blade member 10 may also be provided with an internal passage or passages through which a fluid (generally air) is circulated during operation of the turbine for purposes of cooling the blade. Frequently, the fluid is forced out of holes situated at the leading and trailing edges of the airfoil to effect skin cooling by laminar flow of the g fluid over the surface of the airfoil portion 16.
Details of such cooling provisions are known in the art and are not shown here since they are unnecessary to an understanding of this invention. The art of directionally casting such blades is also known in the art as shown, for example, by U.S. Patent 3,494,709 and, therefore, also shall not be described here in detail.
Following directional solidification, which typically progresses downwardly toward base 12, in the direction indicated by arrow 18, the solidified blade member 10 is inspected for the presence of grain boundaries and verification of the axial growth direction 18. The axial growth direction is determined by X-ray analysis (typically by the well-known Laue method) and for nickel-base superalloys is preferably plus or minus 15 degrees of the ~001] crystal direction.
Heretofore, only low angle grain boundaries, ~o such as the one shown schematically at 20, up to a maximum of about 6 mismatch across adjacent grains have been permitted in single crystal blades 10.
Skilled observers can generally visually detect LABs on the order of 0-3. Towards the maximum permissible mismatch of 6, however, visual techniques become unreliable and additional Laue patterns on either side of the boundary in question must be made. The Laue patterns are not inexpensive and due to current single crystal practice 3 to 4 Laue patterns generally are required per casting. Presently, due in part to uncertainties in detecting low angle grain boundaries, the yield of castings is only about 45-55%.
It has now been discovered that nickel-base superalloys suitable for casting as single crystal 3~ articles can be improved by the addition of small, but controlled, amounts of boron and carbon, and optionally hafnium, yielding a new family of single crystal nickel-base superalloys.
The principal benefit, in addition to an improved balance between cyclic oxidation and hot corrosion resistance, following from this discovery is that low angle grain boundaries in single crystal articles made from the superalloys of the invention herein are stronger than their prior art single crystal articles. Therefore, LABs having greater than 6 of mismatch may be tolerated and accepted in such articles compared to about 6 maximum previously considered acceptable. ~educed inspection costs and increased yield of acceptable articles follows from the aforesaid improved tolerance to low angle grain boundaries. It will be appreciated that neither LABs nor ~ABs will be present in a true "single crystal." It will further be appreciated, however, that although there may be one or more low angle boundaries present in the single crystals discussed herein reference shall still be made to single crystals.
As noted above, single crystal articles such as blade 10 are subjected to an X-ray test to determine orientation and to a visual test to determine the presence (or absence) of high angle grain boundaries.
While the X-ray test must still be used with the new superalloys of this invention to determine orientation, the number of X-ray tests required to distinguish between ~ABs and LABs is expected to be greatly reduced or eliminated.
Stated another way, the tolerance limits for accepting LABs visually can be increased from about 0-3 to about 0-9 for the airfoil articles made from the new superalloys o~ this invention and Laue determinations are only expected to be required for boundaries greater than about 9. It should be noted that large boundary mismatches are acceptable in the new superalloys when compared to the approximately 6 mismatches allowed in the prior art alloys. In the root and platform areas, there will be no limitation on the boundaries, i.e., ~ABs will be acceptable, due to the increased strength of the boundaries in articles made from the superalloys of this invention and in recognition of the lower temperatures in the platform and root portions compared to those in the airfoil portion. Thus, reference to a "single crystal article"
herein shall be to an article at least a portion of which shall be in the nature of a "single crystal."
Overall, the estimated casting yield of articles made from the new superalloys is expected to increase to 75-85~.
It will be appreciated, therefore, that the new superalloys of this invention possess exceptional properties even when processing by DS techniques results in articles having oriented high angle grain boundaries throughout. Exceptional properties are anticipated even when the superalloys of this invention are conventionally cast (CC) to produce articles having a plurality of randomly oriented grains with high angle grain boundaries therebetween.
Accordingly, there is provided by this invention a new family of nickel-base superalloys castable as single crystal articles having improved tolerance to low angle grain boundaries consisting essentially of chromium, cobalt, molybdenum, tungsten, tantalum, titanium, aluminum, columbium, hafnium, carbon, boron and (optionally) hafnium in the percentages (by weight) set forth in Table I, below, the balance being nickel and incidental impurities.
TABLE I
ALLOY CO~lPOSITIO~S
(weight ~) Elements Base Preferred Most Preferred Cr 7-12 7-10 9.5-10.0 ~o S-15 5-10 7.0-8.0 Mo 0.5-5 1-3 1.3-1.7 W 3-12 4-8 5.75-6.25 Ta 2-6 3-5 4.6-5.0 Ti 2-5 3-4 3.4-3.6 Al 3-5 4-4.5 4.1-4.3 Cb 0-2 0-1 0.4-0.6 Hf 0-2.0 0.05-0.5 0.1-0.2 C 0.03-0.25 0.03-0.1 0.05-0.07 B 0.002-0.050 0.002-0.020 0.003-0.005 In Table II there is set forth the co~positions of the various alloys, including those of the present invention, referred to herein.
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Shown schematically in FIG. 2 is the top portion of a slab-like ingot 30 directionally solidified in the direction of arrow 18' to produce material for testing. The material produced was either S a single crystal which had no LA~s or, as depicted in FIG. 2, had at least one LAB 20' parallel to solidification direction 18', or was conventionally DS'd to produce ingots having a plurality of HABs oriented parallel to solidification direction 18' (not illustrated). The ingots produced so as to have a plurality of oriented HABs were likewise produced by the same DS process but without the use of the techniques required to produce single crystals and will be referred to herein simply as DS or DS'd material.
For comparative purposes, some of the alloys of Table I
were also cast conventionally to produce ingots having a plurality of randomly oriented grains with high angle grain boundaries in between.
The heat treatment method used with the superalloys of the present invention to substantially fully develop a duplex gamma prime structure was to slowly heat the as DS'd ingot (or article) to about 2310 F and hold thereat for about 2 hours to place the gamma prime phase into solid solution; cool at a rate of 100 F to 150 F per minute to below about 1975 F
then at a rate of about 75 F to 150 F per minute to about 1200 P; reheat to about 1975 F for about four hours; cool at a rate of about 75 F to lS0 F per minute to about 1200 F; heat to about 1650 F for about 16 hours; and, lastly, cool to ambient temperature.
The aforementioned specimens for physical property measurements were fabricated in conventional fashion from bar-like sections 32 taken transverse to 3762~
solidification direction 18' of the heat treated ingots. Each single crystal specimen from section 32 contained either no JABs or an LAB of ~known orientation established by X-ray analysis. Similarly, specimens from DS'd slabs contained a plurality of oriented grains and oriented high angle grain boundaries and specimens from CC slabs contained a plurality of randomly oriented grains and randomly oriented high angle grain boundaries.
By reference to FIG. 3 and Table III, it may be seen that boron has been discovered, contrary to the teachings of the prior art, to be beneficial to the stress-rupture strength of single crystals and, with carbon, strengthens any LABs present in single crystals made from the alloys of this invention. In FIGS. 3 and 4 and Tables III and IV, reference is made to "~ of Perfect Crystal Life" which is the stress-rupture life of an alloy of the Base composition (Table II) DS'd to form no LABs and tested with its ~110] direction perpendicular to the ~S direction (and parallel to the specimen stress axis) at the same conditions of stress and temperature as the superalloy for which it serves as the comparative standard. Also in some Tables, there is set forth for comparative purposes the 2~ stress-rupture lives of specimens of the Base composition having a LAB with the degree of mismatch shown and for specimens of the Base composition in the DS'd condition.
- 133762~
13D~-8137 TABLE III-A
TRANSV~RSEl STRESS-RUPTURE P~OPERTIES
SIRESS-~UPTU~E PROPERTIES
~ OF
NO. HEAT B Hf LAB TEMP ST~ESS LIFE ELONG A
_ (ppm) (~) (de~) () (ksi) (hrs) (~
1 47 - 0.1512.6 1600 58 24.6 0.4 0.0 2 47 - 0.1511.9 1600 58 10.3 0.6 1.2 3 48 20 0.159.2 1600 58 146.0 0.6 0 4 48 2~ 0.1512.2 1600 58 77.7 1.3 0 50 30 0.2012.03 1600 ~55 175.1 2.4 1.8 6 49 43 0.15 14.0 1500 75 185.02 2.1 2.5 7 49 43 0.15 14.0 1600 58 304.04 3.8 2.5 8 49 43 0.15 ~31 1600 5848.8 1.3 0.6 9 49 43 0.15 ~31 1600 5846.3 1.8 0.6 49 43 0.15 15 1600 58109.8 0.9 1.2 11 59 75 0.20 13.6 1600 58347.9 1.9 1.8 12 90 46 0.15 11 1600 58380.1 3.9 24.9 13 90 46 0.15 14 1600 58171.4 1.8 2.5 14 90 46 0.15 16 1600 58168.0 2.5 3.7 49 40 0.15 14.0 1700 4592.2 2.5 0.7 16 49 43 0.15 14 1800 30108.7 1.9 1.3 17 49 43 0.15 15 1800 24124.7 2.5 0.6 18 49 43 0.15 15 1800 3033.3 0.9 0.0 19 50 30 0.20 123 1800 28234.05 NA NA
90 46 0.15 11 1800 30118.8 2.6 0.6 21 90 46 0.15 14 1800 24296.1 1.8 0 22 90 46 0.15 14 1800 3051.0 1.6 2.5 23 9~ 46 0.15 16 1800 3073.1 3.3 0.8 1 Transverse across LABs (or HABs~ and transverse - to solidification direction.
2 No failure in time shown - was step loaded to 104.8 ksi/3 hrs then step loaded to 134.7 ksi/
failure in 1 min.
3 In radius section of specimen 4 No failure in time shown - s~ep loaded to 78 ksi/
failure in 4.7 addn'l hrs.
NICKEL-BASE SUPERALLOYS FOR PRODUCING
SINGLE CRYSTAL ARTICLES HAVING IMPROVED
TOLERANCE TO LOW ANGLE GRAIN BOUNDARIES
CROSS-REFERENCE TO RELATED APPLICATION
The invention disclosed and claimed herein is related to the invention disclosed and claimed in Canadian Application Serial No. 400,748, filed April 8, 1982.
BACKGROUND OF THE INVENTION
This invention pertains generally to nickel-base superalloys castable as single crystal articles of manufacture, which articles are especially useful as hot-section components of aircraft gas turbine engines, particularly rotating blades.
The efficiency of gas turbine engines depends significantly on the operating temperature of the various engine components with increased operating temperatures resulting in increased efficiencies. The search for increased efficiencies has led to the development of heat-resistant nickel-base superalloys which can withstand increasingly high temperatures yet maintain their basic material properties. The requirement for increased operating temperatures has also lead to the development of highly complex cast hollow shapes, e.g., blades and vanes, which provide efficient cooling of the material used to produce such shapes.
The casting processes used with early generations of nickel-base superalloys, commonly . .
~., ^~
referred to as conventionally cast nickel-base superalloys, generally produced parts whose microstructures consisted of a multitude of equiaxed single crystals (grains) of random ~nonoriented) crystallographic orientation with grain boundaries between the grains. Grain boundaries are regions of highly nonoriented structure only a few atomic diameters wide which serve to accommodate the crystallographic orientation difference or mismatch between adjacent grains.
A high angle grain boundary (HAB) is generally regarded as a boundary between adjacent grains whose crystallographic orientation differs by more than about 5-6 degrees. High angle grain boundaries are regions Of high surface energy, i.e., on the order of several hundreds of ergs/cm2, and of such high random misfit that the structure cannot easily be described or modelled. Due to their high energies and randomness, high angle grain boundaries are highly mobile and are preferential sites for such solid-state reactions as diffusion, precipitation and phase transformations;
thus, high angle boundaries play an important role in the deformation and fracture characteristics and chemical characteristics (e.g., resistance to oxidation and hot corrosion) of polycrystalline metals.
Also, due to the high energies and disorder of HABs, impurity atoms are attracted preferentially (segregated) to high angle grain boundaries to the degree that the concentration of impurity atoms at the grain boundary can be several orders of magnitude greater than the concentration of the same impurity atoms within the grains. The presence of such high concentrations of impurity atoms at high angle grain boundaries can further modify the mechanical and chemical properties of metals. ~or example, in 133~24 13~V-8137 nickel-base superalloys, lead and bismuth are deleterious impurities which segregate to the grain boundaries. At high temperatures, even small amounts (i.e., a few ppm) of such impurities in the grain boundaries of nickel-base superalloys degrade the mechanical properties (e.g., stress-rupture strength) and failure generally occurs at the grain boundaries.
In contrast to high angle grain boundaries, low angle grain boundaries, sometimes also called subgrain boundaries, are generally regarded as boundaries between adjacent grains whose crystallographic orientation differs by less than about 5 degrees. It is to be understood, however, that the classification of a boundary as high angle or low angle may vary depending upon the person or organization doing the classification. For the limiting case of a low angle boundary (LAB) where the orientation difference across the boundary may be less than 1 degree, the boundary may be described (modelled) in terms of a regular array of edge dislocations, i.e., a tilt boundary. While the mismatch is technically that between any two adjacent grains, and not that of the boundary per se, the extent of the mismatch is commonly assigned to the boundary; hence the terminology of, for example, a 5 degree low angle boundary, which usages shall be used herein interchangeably.
Low angle grain boundaries are more highly ordered and have lower surface energies than high angle grain boundaries. Higher order and lower energy result in boundaries with low mobility and low attraction for impurity atoms which, in turn, results in a lesser effect on properties, mechanical and chemical, compared to high angle grain boundaries. Thus, while no grain boundaries constitute a preferred condition, low angle boundaries are to be preferred over high angle grain boundaries.
1~37624 13~V-81a7 Improvements in the ability of conventional superalloys to withstand higher temperatures without impairing other needed qualities, such as strength and oxidation resistance, was achieved through alloy development and the introduction of improved processing techniques. These improvements followed fro~ findings that the strength of such superalloys, and other important characteristics, were dependent upon the strengths of the grain boundaries. To enhance such conventional superalloys, initial efforts were aimed at strengthening the grain boundaries by the addition of vario~s grain boundary strengthening elements such as carbon (C), boron ~B), zirconium (Zr), and hafnium (Hf) and by the removal of deleterious impurities such as lead (Pb) or bismuth (Bi) which tended to segregate at and weaken the grain boundaries.
- Efforts to further increase strength levels in conventional nickel-base superalloys by preferentially orienting the grain boundaries parallel to the growth or solidification direction were subse~uently initiated. Preferential orientation of the grains generally results in a columnar grain structure of long, slender (columnar) grains oriented in a single crystallographic direction and minimizes or eliminates grain boundaries transverse to the growth or solidification direction. The process used, i.e., directional solidification (DS), had long been used for other purposes such as the manufacture of magnets and grain-oriented silicon steel for transformers. That process has been described and impro~ed upon, for instance, in U.S. Patent 3,897,815 - Smashey.
-Compared with conventionally cast superalloy articles, directionally solidified (~S'd) articles exhibited increased strength when the columnar grains were aligned parallel to the principal stress axis due to the elimination or minimization of grain boundaries transverse to the direction of solidification. In addition, DS provided an increase in other properties, such as ductility and resistance to low cycle fatigue, due to the preferred grain orientation. ~owever, reduced strength and ductility properties still existed in the transverse directions due to the presence of longitudinal columnar grain boundaries in such DS'd articles. Additions of Hf, C, B, and Zr were utilized to improve the transverse grain boundary strength of such alloys as was done previously in conventional equiaxed nickel-base superalloys. However, large additions of these elements acted as melting point depressants and resulted in limitations in heat treatment which did not allow the development of maximum strengths within such directionally solidified superalloys.
It has been recognized for some time that articles could be cast in various shapes as a perfect single crystal, thus eliminating grain boundaries altogether. A logical step then was to modify the DS
process to enable solidification of superalloy articles as single crystals to eliminate longitudinally extending high angle grain boundaries previously found in DS'd articles.
In the single crystal metallic alloy arts, it has heretofore been conventional teaching that elements such as boron, zirconium, and carbon are to be avoided, i.e., kept to the lowest levels possible with commercial melting and alloying practice and 35 technology. For example, U.S. Patent 3,494,709 recites - 1337~2~
the deleterious effect of B and ~r, proposing limits of O.U01~ and 0.01~ for those elements, respectively.
U.S. Patent 3,567,526 teaches that the fatigue properties of single crystal superalloy articles can be improved by the complete removal of carbon.
In U.S. Patent 4,116,723, there is disclosed homogeneous single crystal nickel-base superalloy articles having no intentional additions of cobalt (Co), B, Zr or C which are said to have superior mechanical properties, e.g., creep and time to rupture, compared to similar nickel-base superalloys containing Co, C, B, and Zr. Therein it is taught that cobalt should be restricted to less than about 0.5~, and more preferably to less than about 0.2~, to preclude the formation of deleterious topologically close packed phases (TCP) (e.g., ~ and ~). Further, it is taught therein that no single element of the group carbon, boron, and zirconium should be present in an amount greater than 50 ppm, that preferably the total of such impurities be less than 100 ppm and, most preferably, that carbon be kept below 30 ppm and that ~ and Zr each be kept below 20 ppm. In any event, it is taught that carbon must be kept below that amount of carbon which will form MC type carbides. Subse~uently, in U.S.
Patent 4,209,348 it was shown that 3-7~ Co could be included in the single crystal nickel-base superalloys disclosed therein without forming TCP.
Another purpose in limiting C, B, and Zr is to increase the incipient melting temperature in relation to the gamma prime solvus temperature thus permitting solutionizing heat treatments to be performed at temperatures where complete solutionizing of the gamma prime phase is possible in reasonable times without causing localized melting of solute-rich regions.
~ecently, however, it has been recognized, U.S. Patent 4,402,772, that the addition of hafnium in small 133762~
13~V-8137 amounts to certain of nickel-base superalloys for the casting of single crystal articles is effective, for example, in providing enhanced properties and enhanced heat treatability in that such articles have a greater s temperature range between the gamma prime solvus and incipient melting temperatures than do most prior art single crystal articles.
SU~ARY OF THE I~VENTION
There is provided by the present invention nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries. The improved tolerance to low angle grain boundaries arises from the discovery that nickel-base superalloys suitable for casting as single crystal articles can, contrary to the teachings of the prior art, be improved by the addition of small, but controlled, amounts of boron and carbon, and optionally hafnium, and is manifested principally by improved grain boundary strength. Additionally, the superalloys of this invention also possess an improved balance between cyclic oxidation and hot corrosion resistance tue primarily to the carbon and hafnium and an increased Al to Ti ratio.
As one result of this increased grain boundary strength, grain boundary mismatches far greater than the 6 limit for prior art single crystal superalloys can be tolerated in single crystal articles made from the nickel-base superalloys of this invention. This translates, for example, into lower inspection costs and higher yields as grain boundaries over a broader range can be accepted by the usual inspection techniques without resorting to expensive X-ray techniques. The superalloys of this invention are especially useful when directionally solidified as hot-section components of aircraft gas turbine engines, particularly rotating blades.
133~624 Broadly, the single-crystal superalloys of this invention consist essentially of about, by weight, 7-12~ Cr, 5-1~ Co, 0.5-5~ Mo, 3-12~ W, 2-6$ Ta, 2-5 Ti, 3-5~ Al, 0-2~ Cb, 0-2.0~ ~f, 0.03-0.25% C and 0.002-0.050% B, the balance being nickel and incidental impurities.
D~lAILED DESCRIPTION OF THE DRAWINGS
FIGURE 1 is a perspective schematic view of a blade member for use in a gas turbine engine;
FIGURE 2 is a perspective schematic view of a directionally solidified slab-like single crystal ingot marked for removal of blanks to be processed into mechanical property test specimens;
FIGURE 3 is a graph of comparative stress-rupture life versus alloy boron content;
FIGURE 4 is a graph of comparative stress-rupture life versus grain boundary misfit; and FIGURE 5 is a graph of external metal loss in cyclic oxidation as a function of exposure time.
DETAILEV DESCRIPTION OF THE INVENTION
Nickel-base superalloys castable as single crystals have typically been used to manufacture airfoil members, e.g., rotating blades and stationary vanes, for the hot section of aircraft gas turbine engines. ~uch a blade member 10 is shown schematically in FI~. 1 and includes base (or root) portion 12 (shown machined to a "fir-tree" configuration for attachment to a disk), platform portion 14, and aerodynamically curved airfoil portion 16. Blade member 10 may also be provided with an internal passage or passages through which a fluid (generally air) is circulated during operation of the turbine for purposes of cooling the blade. Frequently, the fluid is forced out of holes situated at the leading and trailing edges of the airfoil to effect skin cooling by laminar flow of the g fluid over the surface of the airfoil portion 16.
Details of such cooling provisions are known in the art and are not shown here since they are unnecessary to an understanding of this invention. The art of directionally casting such blades is also known in the art as shown, for example, by U.S. Patent 3,494,709 and, therefore, also shall not be described here in detail.
Following directional solidification, which typically progresses downwardly toward base 12, in the direction indicated by arrow 18, the solidified blade member 10 is inspected for the presence of grain boundaries and verification of the axial growth direction 18. The axial growth direction is determined by X-ray analysis (typically by the well-known Laue method) and for nickel-base superalloys is preferably plus or minus 15 degrees of the ~001] crystal direction.
Heretofore, only low angle grain boundaries, ~o such as the one shown schematically at 20, up to a maximum of about 6 mismatch across adjacent grains have been permitted in single crystal blades 10.
Skilled observers can generally visually detect LABs on the order of 0-3. Towards the maximum permissible mismatch of 6, however, visual techniques become unreliable and additional Laue patterns on either side of the boundary in question must be made. The Laue patterns are not inexpensive and due to current single crystal practice 3 to 4 Laue patterns generally are required per casting. Presently, due in part to uncertainties in detecting low angle grain boundaries, the yield of castings is only about 45-55%.
It has now been discovered that nickel-base superalloys suitable for casting as single crystal 3~ articles can be improved by the addition of small, but controlled, amounts of boron and carbon, and optionally hafnium, yielding a new family of single crystal nickel-base superalloys.
The principal benefit, in addition to an improved balance between cyclic oxidation and hot corrosion resistance, following from this discovery is that low angle grain boundaries in single crystal articles made from the superalloys of the invention herein are stronger than their prior art single crystal articles. Therefore, LABs having greater than 6 of mismatch may be tolerated and accepted in such articles compared to about 6 maximum previously considered acceptable. ~educed inspection costs and increased yield of acceptable articles follows from the aforesaid improved tolerance to low angle grain boundaries. It will be appreciated that neither LABs nor ~ABs will be present in a true "single crystal." It will further be appreciated, however, that although there may be one or more low angle boundaries present in the single crystals discussed herein reference shall still be made to single crystals.
As noted above, single crystal articles such as blade 10 are subjected to an X-ray test to determine orientation and to a visual test to determine the presence (or absence) of high angle grain boundaries.
While the X-ray test must still be used with the new superalloys of this invention to determine orientation, the number of X-ray tests required to distinguish between ~ABs and LABs is expected to be greatly reduced or eliminated.
Stated another way, the tolerance limits for accepting LABs visually can be increased from about 0-3 to about 0-9 for the airfoil articles made from the new superalloys o~ this invention and Laue determinations are only expected to be required for boundaries greater than about 9. It should be noted that large boundary mismatches are acceptable in the new superalloys when compared to the approximately 6 mismatches allowed in the prior art alloys. In the root and platform areas, there will be no limitation on the boundaries, i.e., ~ABs will be acceptable, due to the increased strength of the boundaries in articles made from the superalloys of this invention and in recognition of the lower temperatures in the platform and root portions compared to those in the airfoil portion. Thus, reference to a "single crystal article"
herein shall be to an article at least a portion of which shall be in the nature of a "single crystal."
Overall, the estimated casting yield of articles made from the new superalloys is expected to increase to 75-85~.
It will be appreciated, therefore, that the new superalloys of this invention possess exceptional properties even when processing by DS techniques results in articles having oriented high angle grain boundaries throughout. Exceptional properties are anticipated even when the superalloys of this invention are conventionally cast (CC) to produce articles having a plurality of randomly oriented grains with high angle grain boundaries therebetween.
Accordingly, there is provided by this invention a new family of nickel-base superalloys castable as single crystal articles having improved tolerance to low angle grain boundaries consisting essentially of chromium, cobalt, molybdenum, tungsten, tantalum, titanium, aluminum, columbium, hafnium, carbon, boron and (optionally) hafnium in the percentages (by weight) set forth in Table I, below, the balance being nickel and incidental impurities.
TABLE I
ALLOY CO~lPOSITIO~S
(weight ~) Elements Base Preferred Most Preferred Cr 7-12 7-10 9.5-10.0 ~o S-15 5-10 7.0-8.0 Mo 0.5-5 1-3 1.3-1.7 W 3-12 4-8 5.75-6.25 Ta 2-6 3-5 4.6-5.0 Ti 2-5 3-4 3.4-3.6 Al 3-5 4-4.5 4.1-4.3 Cb 0-2 0-1 0.4-0.6 Hf 0-2.0 0.05-0.5 0.1-0.2 C 0.03-0.25 0.03-0.1 0.05-0.07 B 0.002-0.050 0.002-0.020 0.003-0.005 In Table II there is set forth the co~positions of the various alloys, including those of the present invention, referred to herein.
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Shown schematically in FIG. 2 is the top portion of a slab-like ingot 30 directionally solidified in the direction of arrow 18' to produce material for testing. The material produced was either S a single crystal which had no LA~s or, as depicted in FIG. 2, had at least one LAB 20' parallel to solidification direction 18', or was conventionally DS'd to produce ingots having a plurality of HABs oriented parallel to solidification direction 18' (not illustrated). The ingots produced so as to have a plurality of oriented HABs were likewise produced by the same DS process but without the use of the techniques required to produce single crystals and will be referred to herein simply as DS or DS'd material.
For comparative purposes, some of the alloys of Table I
were also cast conventionally to produce ingots having a plurality of randomly oriented grains with high angle grain boundaries in between.
The heat treatment method used with the superalloys of the present invention to substantially fully develop a duplex gamma prime structure was to slowly heat the as DS'd ingot (or article) to about 2310 F and hold thereat for about 2 hours to place the gamma prime phase into solid solution; cool at a rate of 100 F to 150 F per minute to below about 1975 F
then at a rate of about 75 F to 150 F per minute to about 1200 P; reheat to about 1975 F for about four hours; cool at a rate of about 75 F to lS0 F per minute to about 1200 F; heat to about 1650 F for about 16 hours; and, lastly, cool to ambient temperature.
The aforementioned specimens for physical property measurements were fabricated in conventional fashion from bar-like sections 32 taken transverse to 3762~
solidification direction 18' of the heat treated ingots. Each single crystal specimen from section 32 contained either no JABs or an LAB of ~known orientation established by X-ray analysis. Similarly, specimens from DS'd slabs contained a plurality of oriented grains and oriented high angle grain boundaries and specimens from CC slabs contained a plurality of randomly oriented grains and randomly oriented high angle grain boundaries.
By reference to FIG. 3 and Table III, it may be seen that boron has been discovered, contrary to the teachings of the prior art, to be beneficial to the stress-rupture strength of single crystals and, with carbon, strengthens any LABs present in single crystals made from the alloys of this invention. In FIGS. 3 and 4 and Tables III and IV, reference is made to "~ of Perfect Crystal Life" which is the stress-rupture life of an alloy of the Base composition (Table II) DS'd to form no LABs and tested with its ~110] direction perpendicular to the ~S direction (and parallel to the specimen stress axis) at the same conditions of stress and temperature as the superalloy for which it serves as the comparative standard. Also in some Tables, there is set forth for comparative purposes the 2~ stress-rupture lives of specimens of the Base composition having a LAB with the degree of mismatch shown and for specimens of the Base composition in the DS'd condition.
- 133762~
13D~-8137 TABLE III-A
TRANSV~RSEl STRESS-RUPTURE P~OPERTIES
SIRESS-~UPTU~E PROPERTIES
~ OF
NO. HEAT B Hf LAB TEMP ST~ESS LIFE ELONG A
_ (ppm) (~) (de~) () (ksi) (hrs) (~
1 47 - 0.1512.6 1600 58 24.6 0.4 0.0 2 47 - 0.1511.9 1600 58 10.3 0.6 1.2 3 48 20 0.159.2 1600 58 146.0 0.6 0 4 48 2~ 0.1512.2 1600 58 77.7 1.3 0 50 30 0.2012.03 1600 ~55 175.1 2.4 1.8 6 49 43 0.15 14.0 1500 75 185.02 2.1 2.5 7 49 43 0.15 14.0 1600 58 304.04 3.8 2.5 8 49 43 0.15 ~31 1600 5848.8 1.3 0.6 9 49 43 0.15 ~31 1600 5846.3 1.8 0.6 49 43 0.15 15 1600 58109.8 0.9 1.2 11 59 75 0.20 13.6 1600 58347.9 1.9 1.8 12 90 46 0.15 11 1600 58380.1 3.9 24.9 13 90 46 0.15 14 1600 58171.4 1.8 2.5 14 90 46 0.15 16 1600 58168.0 2.5 3.7 49 40 0.15 14.0 1700 4592.2 2.5 0.7 16 49 43 0.15 14 1800 30108.7 1.9 1.3 17 49 43 0.15 15 1800 24124.7 2.5 0.6 18 49 43 0.15 15 1800 3033.3 0.9 0.0 19 50 30 0.20 123 1800 28234.05 NA NA
90 46 0.15 11 1800 30118.8 2.6 0.6 21 90 46 0.15 14 1800 24296.1 1.8 0 22 90 46 0.15 14 1800 3051.0 1.6 2.5 23 9~ 46 0.15 16 1800 3073.1 3.3 0.8 1 Transverse across LABs (or HABs~ and transverse - to solidification direction.
2 No failure in time shown - was step loaded to 104.8 ksi/3 hrs then step loaded to 134.7 ksi/
failure in 1 min.
3 In radius section of specimen 4 No failure in time shown - s~ep loaded to 78 ksi/
failure in 4.7 addn'l hrs.
5 No failure in time shown - step loaded to 50 ksi/failure.
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-That the superalloys of the invention have superior stress-rupture strengths compared to conventional single crystal superalloys at any given angle of mismatch from O to about 18 is shown in FIG.
4. Similarly, at any given level of ~ of no LAB
rupture life the superalloys of the invention can tolerate larger degrees of misfit, on the order of about 2 times, than can single crystal superalloys of the prior art. As may be noted from Table IV, even when ~S'd to form HABs, the superalloys of the inrention have superior str r" " "
/
133762~
13~V-8137 ~ABLE IV
ST~ESS-RUPTURE STRENGTHS1 (DS'd High Angle Boundary Specimens) COMPARATIVE
STKESS-RUPTURE
LIV~S (H~S) ST~ESS-RUPTUXE P~UPERTIES ~A~E
R UF NO DS CC
H~AT B TEMP STRESS LIFE ELONG A LAB ~ASE R80 (ppm) () (ksi) (hrs) (%) (~) 110 47 0 1400 90 4.0 0.9 0.0 220 NA 100 1600 55 1.9 1.0 ~.0 230 ~3 45 18U0 26 2.3 2.1 2.7 250 cl 65 2000 12 3.1 1.0 0.0 250 c4 10 48 20 1400 90 3.3 0.8 0.0 220 NA 100 1600 5515.6 ~.6 0.8 230 c3 4S
1800 26 9.2 1.1 0.0 250 ~1 65 2000 12 4.5 0.0 0.0 250 c4 10 1400 90 184.42 1.9 3.8 220 NA 100 1600 55 69.2 1.5 0.0 230 c3 45 1800 26 65.6 1.0 0.0 250 ~1 65 2000 12 9.1 1.6 1.3 25~ c4 10 49 43 1400 90 92.53 3.7 6.2 220 NA 100 1600 55 133.8 1.3 2.5 230 c3 45 1800 2650.0 1.2 0.0 250 cl 65 2000 12 2.9 1.9 2.0 250 c4 10 2000 12 1.8 NA 0.0 250 c4 10 59 75 1400 90 92.44 10.8 32.0 220 N~ 100 1600 55 54.1 0.9 0.0 230 c3 45 1800 26 98.1 1.7 0.6 250 ~1 6S
2000 12 4.1 NA 0.6 250 c4 10 AA - 1600 50 0.3 1 All transverse to DS direction except for CC
35 2Step Loaded 3Step Loaded 4Step Loaded to 100 KSI to 110 KSI + 110 KSI + 21.8 hrs + 2.2 hrs 21.9 hrs 120 KSI +2.2 hrs to 110 KSI 120 KSI + 2.1 hrs 130 KSI +.1 hrs + .8 hrs 130 KSI + .2 hrs 140 KSI +.2 hrs to 120 KSI 140 KSI + 1.3 + .2 hrs 150 KSI + .3 hrs 133~ 624 -Table V presents the results of cyclic oxidation tests on uncoated 1/4" x 3" long round pin specimens conducted under the conditions shown in the table using a natural gas flame at Mach 1 gas velocity. The specimens were rotated for uniform exposure and cycled out of the flame once per hour to cool the specimens to room temperature. External metal loss was measured on a section cut transverse to the length dimension of the specimen. Metal loss per side was found by dividing the difference between the pin diameter before and after test by two. The data in the table are the average of two such measurements at 90 to each other across the diameter of the specimen.
The data of Table V are presented in graphical form in FIG. 5. It may be noted that while the resistance of the superalloys of the invention to cyclic oxidation is not as good as exemplary alloy BB, the superalloys of the invention possess highly acceptable resistance to cyclic oxidation which is an improvement over the cyclic oxidation resistance of the Base alloy and R125. The improved cyclic oxidation resistance of the superalloys of this invention compared to that of the Base superalloy is believed to be due primarily to the increased Al to Ti ratio.
Comparison of the data for heats 44 and 49/50 shows the further increased cyclic oxidation resistance provided by the addition of hafnium.
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Table VI presents the results of hot corrosion tests on uncoated 1/8" x 2" long round pin specimens conducted under the conditions shown in the table using a JP-5 fuel-fired flame with salt in parts per million (ppm) shown added to the combustion products. The specimens were rotated for uniform exposure and were cycled out of the flame to room temperature once every day. The data of Table VI show that the presence of carbon in the superalloys of the invention is required for hot corrosion resistance and that the hot corrosion resistance of the superalloys of the invention is superior to that of alloys AA and BB - prior art single crystal alloys.
The superalloys of the invention thus have an improved balance between cyclic oxidation and hot corrosion resistance due primarily to the carbon and hafnium and an increased Al to Ti ratio in comparison to the Base alloy.
TABLE ~I
HOT COXROSION TESTS
TEMP SALT TIME METAL L~SS
- HEAT ~) (ppm) (Hrs) (mils/side) 44 1600 1 613 1.7 Base 1600 1 613 1.0 25 18 1600 2 402 36.0 44 1600 2 620 1.0 Base 1600 2 620 1.5 AA 1600 2 470 11.8 BB 1600 2 620 28.0 30 44 1700 5 478 6.6 Base 1700 5 478 11.3 AA 1700 5 478 30.1 There being extant evidence that the inventive concepts herein of adding small, but controlled, amounts of boron and carbon, and optionally hafnium, to improve the low angle grain boundary tolerance of nickel-base superalloys suitable for casting as single crystal articles are applicable to other nickel-base single crystal superalloys, it will be understood that various changes and modifications not specifically referred to herein may be made in the invention herein described, and to its uses herein described, without departing from the spirit of the invention particularly as defined in the following claims.
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-That the superalloys of the invention have superior stress-rupture strengths compared to conventional single crystal superalloys at any given angle of mismatch from O to about 18 is shown in FIG.
4. Similarly, at any given level of ~ of no LAB
rupture life the superalloys of the invention can tolerate larger degrees of misfit, on the order of about 2 times, than can single crystal superalloys of the prior art. As may be noted from Table IV, even when ~S'd to form HABs, the superalloys of the inrention have superior str r" " "
/
133762~
13~V-8137 ~ABLE IV
ST~ESS-RUPTURE STRENGTHS1 (DS'd High Angle Boundary Specimens) COMPARATIVE
STKESS-RUPTURE
LIV~S (H~S) ST~ESS-RUPTUXE P~UPERTIES ~A~E
R UF NO DS CC
H~AT B TEMP STRESS LIFE ELONG A LAB ~ASE R80 (ppm) () (ksi) (hrs) (%) (~) 110 47 0 1400 90 4.0 0.9 0.0 220 NA 100 1600 55 1.9 1.0 ~.0 230 ~3 45 18U0 26 2.3 2.1 2.7 250 cl 65 2000 12 3.1 1.0 0.0 250 c4 10 48 20 1400 90 3.3 0.8 0.0 220 NA 100 1600 5515.6 ~.6 0.8 230 c3 4S
1800 26 9.2 1.1 0.0 250 ~1 65 2000 12 4.5 0.0 0.0 250 c4 10 1400 90 184.42 1.9 3.8 220 NA 100 1600 55 69.2 1.5 0.0 230 c3 45 1800 26 65.6 1.0 0.0 250 ~1 65 2000 12 9.1 1.6 1.3 25~ c4 10 49 43 1400 90 92.53 3.7 6.2 220 NA 100 1600 55 133.8 1.3 2.5 230 c3 45 1800 2650.0 1.2 0.0 250 cl 65 2000 12 2.9 1.9 2.0 250 c4 10 2000 12 1.8 NA 0.0 250 c4 10 59 75 1400 90 92.44 10.8 32.0 220 N~ 100 1600 55 54.1 0.9 0.0 230 c3 45 1800 26 98.1 1.7 0.6 250 ~1 6S
2000 12 4.1 NA 0.6 250 c4 10 AA - 1600 50 0.3 1 All transverse to DS direction except for CC
35 2Step Loaded 3Step Loaded 4Step Loaded to 100 KSI to 110 KSI + 110 KSI + 21.8 hrs + 2.2 hrs 21.9 hrs 120 KSI +2.2 hrs to 110 KSI 120 KSI + 2.1 hrs 130 KSI +.1 hrs + .8 hrs 130 KSI + .2 hrs 140 KSI +.2 hrs to 120 KSI 140 KSI + 1.3 + .2 hrs 150 KSI + .3 hrs 133~ 624 -Table V presents the results of cyclic oxidation tests on uncoated 1/4" x 3" long round pin specimens conducted under the conditions shown in the table using a natural gas flame at Mach 1 gas velocity. The specimens were rotated for uniform exposure and cycled out of the flame once per hour to cool the specimens to room temperature. External metal loss was measured on a section cut transverse to the length dimension of the specimen. Metal loss per side was found by dividing the difference between the pin diameter before and after test by two. The data in the table are the average of two such measurements at 90 to each other across the diameter of the specimen.
The data of Table V are presented in graphical form in FIG. 5. It may be noted that while the resistance of the superalloys of the invention to cyclic oxidation is not as good as exemplary alloy BB, the superalloys of the invention possess highly acceptable resistance to cyclic oxidation which is an improvement over the cyclic oxidation resistance of the Base alloy and R125. The improved cyclic oxidation resistance of the superalloys of this invention compared to that of the Base superalloy is believed to be due primarily to the increased Al to Ti ratio.
Comparison of the data for heats 44 and 49/50 shows the further increased cyclic oxidation resistance provided by the addition of hafnium.
133~624 O U~ ~ O N ¢~
N N N N ~ 1~ 0 N
O
a:~
_ U~
O N O O U~ U~ O
O . . . .
C~ O -- --~ O ~O O
_ U~ 0 0 ~
. .. . .
a~ ~ o ~1 _ N N N N
C
U~
--~ U7 --I ~ ~ 1~ 1`~ ~ 0 u~ 0 Ir~ 0 O _I 0 tD r 1'~ 0 Z~_o O
~n ~ .
-- T ~ ~
C~ ~: o ~ ~
-- X ~ 1--C 1~ N
O ~ l_ ~ . . .. . .
~L~ -- OO N~O _ J ~ J _I
O ~-) 7' E
- ~ ~ O ~
_ r~ ~ Q
_ ~
C
N O O
3 ~nUl O O O O U~
~I) O
....~.. alCl O ~ O O C`~
N C~
o O O O O o O O O O O O ~ _ -- O
N N C~ C~ N N
c51~ 0 0~ U~ CC 1~ 0 ~ O 0~ ~n N ~:
T m m c~ _ N
o In O
N
Table VI presents the results of hot corrosion tests on uncoated 1/8" x 2" long round pin specimens conducted under the conditions shown in the table using a JP-5 fuel-fired flame with salt in parts per million (ppm) shown added to the combustion products. The specimens were rotated for uniform exposure and were cycled out of the flame to room temperature once every day. The data of Table VI show that the presence of carbon in the superalloys of the invention is required for hot corrosion resistance and that the hot corrosion resistance of the superalloys of the invention is superior to that of alloys AA and BB - prior art single crystal alloys.
The superalloys of the invention thus have an improved balance between cyclic oxidation and hot corrosion resistance due primarily to the carbon and hafnium and an increased Al to Ti ratio in comparison to the Base alloy.
TABLE ~I
HOT COXROSION TESTS
TEMP SALT TIME METAL L~SS
- HEAT ~) (ppm) (Hrs) (mils/side) 44 1600 1 613 1.7 Base 1600 1 613 1.0 25 18 1600 2 402 36.0 44 1600 2 620 1.0 Base 1600 2 620 1.5 AA 1600 2 470 11.8 BB 1600 2 620 28.0 30 44 1700 5 478 6.6 Base 1700 5 478 11.3 AA 1700 5 478 30.1 There being extant evidence that the inventive concepts herein of adding small, but controlled, amounts of boron and carbon, and optionally hafnium, to improve the low angle grain boundary tolerance of nickel-base superalloys suitable for casting as single crystal articles are applicable to other nickel-base single crystal superalloys, it will be understood that various changes and modifications not specifically referred to herein may be made in the invention herein described, and to its uses herein described, without departing from the spirit of the invention particularly as defined in the following claims.
Claims (15)
1. A nickel-base superalloy consisting essentially of, in percentages by weight, 7-10 Cr, 5-10 Co, 1-3 Mo, 4-8 W, 3-5 Ta, 3-4 Ti, 4-4.5 Al, 0.4-1 Cb, 0.05-0.5 Hf, 0.03-0.1 C and 0.002-0.020 B, the balance being nickel and incidental impurities.
2. The superalloy of claim 1 consisting essentially of, in percentages 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.
3. A single crystal article of manufacture the overall composition of which is a nickel-base superalloy consisting essentially of, in percentages by weight, 7-10 Cr, 5-10 Co, 1-3 Mo, 4-8 W, 3-5 Ta, 3-4 Ti, 4-4.5 Al, 0-1 Cb, 0.05-0.5 Hf, 0.03-0.1 C and 0.002-0.020 B, the balance being nickel and incidental impurities, wherein any low angle grain boundaries present in said article are greater than about 0°.
and 0.003-0.005 B, the balance being nickel and incidental impurities.
3. A single crystal article of manufacture the overall composition of which is a nickel-base superalloy consisting essentially of, in percentages by weight, 7-10 Cr, 5-10 Co, 1-3 Mo, 4-8 W, 3-5 Ta, 3-4 Ti, 4-4.5 Al, 0-1 Cb, 0.05-0.5 Hf, 0.03-0.1 C and 0.002-0.020 B, the balance being nickel and incidental impurities, wherein any low angle grain boundaries present in said article are greater than about 0°.
4. The article of claim 3 wherein any low angle grain boundaries present therein are in the range of from about 0 to about 20°.
5. The article of claim 4 which is an airfoil member for a gas turbine engine.
6. The article of claim 3 consisting essentially of, in percentages 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.
7. An article of manufacture the overall composition of which is a nickel-base superalloy consisting essentially of, in percentages by weight, 7-10 Cr, 5-10 Co, 1-3 Mo, 4-8 W, 3-5 Ta, 3-4 Ti, 4-4.5 Al, 0-1 Cb, 0.05-0.5 Hf, 0.03-0.1 C and 0.002-0.020 B, the balance being nickel and incidental impurities, at least a portion of which is a single crystal.
and 0.003-0.005 B, the balance being nickel and incidental impurities.
7. An article of manufacture the overall composition of which is a nickel-base superalloy consisting essentially of, in percentages by weight, 7-10 Cr, 5-10 Co, 1-3 Mo, 4-8 W, 3-5 Ta, 3-4 Ti, 4-4.5 Al, 0-1 Cb, 0.05-0.5 Hf, 0.03-0.1 C and 0.002-0.020 B, the balance being nickel and incidental impurities, at least a portion of which is a single crystal.
8. The article of claim 7 wherein any low angle grain boundaries present in said single crystal portion are greater than about 0°.
9. The article of claim 8 wherein any low angle grain boundaries present in said single crystal portion are in the range of from about 0 to about 20°.
10. The article of claim 8 which is an airfoil member for a gas turbine engine at least the airfoil portion of which is said single crystal portion.
11. The article of claim 7 consisting essentially of, in percentages 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.
and 0.003-0.005 B, the balance being nickel and incidental impurities.
12. An article of manufacture the overall composition of which is a nickel-base superalloy consisting essentially of, in percentages by weight, 7-10 Cr, 5-10 Co, 1-3 Mo, 4-8 W, 3-5 Ta, 3-4 Ti, 4-4.5 Al, 0.4-1 Cb, 0.05-0.5 Hf, 0.03-0.1 C and 0.002-0.020 B, the balance being nickel and incidental impurities.
13. The article of claim 12 which is directionally solidified.
14. The article of claim 12 which is conventionally cast.
15. The article of claim 12 wherein said composition consists essentially of, in percentages 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.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8607773A GB2234521B (en) | 1986-03-27 | 1986-03-27 | Nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries |
| DE3612628A DE3612628C2 (en) | 1986-03-27 | 1986-04-15 | Cast workpieces and cast single-crystal workpieces made of superalloys based on nickel for the production of single-crystal objects with improved small-angle grain boundary tolerance |
| FR8605809A FR2731714B1 (en) | 1986-03-27 | 1986-04-22 | NICKEL-BASED SUPERALLOYS FOR THE PRODUCTION OF SINGLE-CRYSTALLINE ARTICLES WITH IMPROVED TOLERANCE TO LOW DISORIENTATION GRAIN BOUNDARIES |
| CA000516576A CA1337624C (en) | 1986-03-27 | 1986-08-22 | Nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries |
| JP80001689A JP3402603B2 (en) | 1986-03-27 | 1989-05-30 | Nickel-base-superalloy with improved low angle grain boundary resistance for producing single crystal products |
| IL9163389A IL91633A (en) | 1986-03-27 | 1989-09-14 | Nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries |
| AU41640/89A AU626581B2 (en) | 1986-03-27 | 1989-09-20 | Nickel-base single crystal superalloys |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8607773A GB2234521B (en) | 1986-03-27 | 1986-03-27 | Nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries |
| DE3612628A DE3612628C2 (en) | 1986-03-27 | 1986-04-15 | Cast workpieces and cast single-crystal workpieces made of superalloys based on nickel for the production of single-crystal objects with improved small-angle grain boundary tolerance |
| FR8605809A FR2731714B1 (en) | 1986-03-27 | 1986-04-22 | NICKEL-BASED SUPERALLOYS FOR THE PRODUCTION OF SINGLE-CRYSTALLINE ARTICLES WITH IMPROVED TOLERANCE TO LOW DISORIENTATION GRAIN BOUNDARIES |
| CA000516576A CA1337624C (en) | 1986-03-27 | 1986-08-22 | Nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries |
| IL9163389A IL91633A (en) | 1986-03-27 | 1989-09-14 | Nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1337624C true CA1337624C (en) | 1995-11-28 |
Family
ID=27508252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000516576A Expired - Fee Related CA1337624C (en) | 1986-03-27 | 1986-08-22 | Nickel-base superalloys for producing single crystal articles having improved tolerance to low angle grain boundaries |
Country Status (6)
| Country | Link |
|---|---|
| AU (1) | AU626581B2 (en) |
| CA (1) | CA1337624C (en) |
| DE (1) | DE3612628C2 (en) |
| FR (1) | FR2731714B1 (en) |
| GB (1) | GB2234521B (en) |
| IL (1) | IL91633A (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5366695A (en) * | 1992-06-29 | 1994-11-22 | Cannon-Muskegon Corporation | Single crystal nickel-based superalloy |
| DE4323486C2 (en) * | 1992-07-23 | 2001-09-27 | Abb Research Ltd | Precipitation-hardenable nickel-based superalloy and use of the alloy as a material in the production of a directional solidified component, such as in particular a gas turbine blade |
| US5549765A (en) * | 1993-03-18 | 1996-08-27 | Howmet Corporation | Clean single crystal nickel base superalloy |
| EP0637476B1 (en) * | 1993-08-06 | 2000-02-23 | Hitachi, Ltd. | Blade for gas turbine, manufacturing method of the same, and gas turbine including the blade |
| FR2712307B1 (en) * | 1993-11-10 | 1996-09-27 | United Technologies Corp | Articles made of super-alloy with high mechanical and cracking resistance and their manufacturing process. |
| US5489346A (en) * | 1994-05-03 | 1996-02-06 | Sps Technologies, Inc. | Hot corrosion resistant single crystal nickel-based superalloys |
| EP0763604B1 (en) * | 1995-09-18 | 2007-08-22 | Howmet Corporation | Clean single crystal nickel base superalloy |
| WO1999067435A1 (en) * | 1998-06-23 | 1999-12-29 | Siemens Aktiengesellschaft | Directionally solidified casting with improved transverse stress rupture strength |
| EP1054072B1 (en) | 1999-05-20 | 2003-04-02 | ALSTOM (Switzerland) Ltd | Nickel base superalloy |
| DE69914741T2 (en) | 1999-08-09 | 2005-01-13 | Alstom (Switzerland) Ltd. | A method of reinforcing the grain boundaries of a Ni-based superalloy component |
| EP1211336B1 (en) * | 2000-11-30 | 2007-05-30 | ONERA (Office National d'Etudes et de Recherches Aérospatiales) | Nickel based superalloy for single crystal turbine blades of industrial turbines having a high resistance to hot corrosion |
| US6558119B2 (en) * | 2001-05-29 | 2003-05-06 | General Electric Company | Turbine airfoil with separately formed tip and method for manufacture and repair thereof |
| CH695497A5 (en) * | 2002-04-30 | 2006-06-15 | Alstom Technology Ltd | Nickel-base superalloy. |
| JP4036091B2 (en) † | 2002-12-17 | 2008-01-23 | 株式会社日立製作所 | Nickel-base heat-resistant alloy and gas turbine blade |
| AU2003255216B8 (en) * | 2003-10-21 | 2008-05-01 | Ansaldo Energia Ip Uk Limited | Nickel-base superalloy |
| DE10361882B4 (en) * | 2003-12-19 | 2013-08-22 | Rolls-Royce Deutschland Ltd & Co Kg | Rotor for the high-pressure turbine of an aircraft engine |
| ES2444407T3 (en) | 2006-09-07 | 2014-02-24 | Alstom Technology Ltd | Procedure for heat treatment of nickel-based super-alloys |
| US20120070303A1 (en) | 2009-08-10 | 2012-03-22 | Yasuhiro Aoki | Ni-BASED SINGLE CRYSTAL SUPERALLOY AND TURBINE BLADE |
| CH702642A1 (en) | 2010-02-05 | 2011-08-15 | Alstom Technology Ltd | Nickel-base superalloy with improved degradation. |
| EP2876176B1 (en) | 2013-11-25 | 2017-06-21 | Mitsubishi Hitachi Power Systems, Ltd. | Ni-based casting superalloy and cast article therefrom |
| JP6528926B2 (en) | 2014-05-21 | 2019-06-12 | 株式会社Ihi | Rotating equipment of nuclear facilities |
| EP2949768B1 (en) * | 2014-05-28 | 2019-07-17 | Ansaldo Energia IP UK Limited | Gamma prime precipitation strengthened nickel-base superalloy for use in powder based additive manufacturing process |
| US10577679B1 (en) * | 2018-12-04 | 2020-03-03 | General Electric Company | Gamma prime strengthened nickel superalloy for additive manufacturing |
| CN113186431A (en) * | 2021-05-06 | 2021-07-30 | 哈尔滨工业大学（深圳） | Nickel-based high-temperature alloy powder suitable for powder metallurgy and preparation method thereof |
| FR3139197A1 (en) * | 2022-08-25 | 2024-03-01 | Safran | Process for controlling the crystalline state of a monocrystalline foundry part |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3494709A (en) * | 1965-05-27 | 1970-02-10 | United Aircraft Corp | Single crystal metallic part |
| US3567526A (en) * | 1968-05-01 | 1971-03-02 | United Aircraft Corp | Limitation of carbon in single crystal or columnar-grained nickel base superalloys |
| IL42133A (en) * | 1972-06-09 | 1975-12-31 | Gen Electric | Nickel base alloy |
| GB1449273A (en) * | 1973-07-25 | 1976-09-15 | Gen Electric | Heat treatment of alloys |
| US3897815A (en) * | 1973-11-01 | 1975-08-05 | Gen Electric | Apparatus and method for directional solidification |
| US4116723A (en) * | 1976-11-17 | 1978-09-26 | United Technologies Corporation | Heat treated superalloy single crystal article and process |
| US4206348A (en) * | 1978-06-05 | 1980-06-03 | Eastman Kodak Company | Optical scanner with electrooptical feedback for beam positioning |
| GB2071695A (en) * | 1980-03-13 | 1981-09-23 | Rolls Royce | An alloy suitable for making single-crystal castings and a casting made thereof |
| US4402772A (en) * | 1981-09-14 | 1983-09-06 | United Technologies Corporation | Superalloy single crystal articles |
| IL65897A0 (en) * | 1981-10-02 | 1982-08-31 | Gen Electric | Single crystal nickel-base superalloy,article and method for making |
| US4475980A (en) * | 1982-06-01 | 1984-10-09 | United Technologies Corporation | Solid state production of multiple single crystal articles |
| US4574015A (en) * | 1983-12-27 | 1986-03-04 | United Technologies Corporation | Nickle base superalloy articles and method for making |
| CA1291350C (en) * | 1986-04-03 | 1991-10-29 | United Technologies Corporation | Single crystal articles having reduced anisotropy |
-
1986
- 1986-03-27 GB GB8607773A patent/GB2234521B/en not_active Expired - Lifetime
- 1986-04-15 DE DE3612628A patent/DE3612628C2/en not_active Expired - Lifetime
- 1986-04-22 FR FR8605809A patent/FR2731714B1/en not_active Expired - Lifetime
- 1986-08-22 CA CA000516576A patent/CA1337624C/en not_active Expired - Fee Related
-
1989
- 1989-09-14 IL IL9163389A patent/IL91633A/en not_active IP Right Cessation
- 1989-09-20 AU AU41640/89A patent/AU626581B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| DE3612628C2 (en) | 2001-11-08 |
| IL91633A (en) | 1994-11-11 |
| DE3612628A1 (en) | 1998-11-05 |
| FR2731714B1 (en) | 1997-08-14 |
| GB2234521A (en) | 1991-02-06 |
| AU4164089A (en) | 1991-03-28 |
| AU626581B2 (en) | 1992-08-06 |
| GB2234521B (en) | 1991-05-01 |
| FR2731714A1 (en) | 1996-09-20 |
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