US20210180158A1 - Ni-Based Superalloy Powder for Additive Manufacturing and an Article Made Therefrom - Google Patents

Ni-Based Superalloy Powder for Additive Manufacturing and an Article Made Therefrom Download PDF

Info

Publication number
US20210180158A1
US20210180158A1 US16/750,745 US202016750745A US2021180158A1 US 20210180158 A1 US20210180158 A1 US 20210180158A1 US 202016750745 A US202016750745 A US 202016750745A US 2021180158 A1 US2021180158 A1 US 2021180158A1
Authority
US
United States
Prior art keywords
alloy
max
nickel
balance
usual impurities
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US16/750,745
Inventor
Ning Zhou
Kyle B. Stritch
Tao Wang
Stephane A.J. Forsik
Gian A. Colombo
Samuel J. Kernion
Mario E. Epler
Austin Dicus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CRS Holdings LLC
Original Assignee
CRS Holdings LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CRS Holdings LLC filed Critical CRS Holdings LLC
Priority to US16/750,745 priority Critical patent/US20210180158A1/en
Assigned to CRS HOLDINGS, INC. reassignment CRS HOLDINGS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KERNION, SAMUEL J., DICUS, Austin, STRITCH, KYLE B., COLOMBO, GIAN A., EPLER, MARIO E., FORSIK, STEPHANE A.J., WANG, TAO, ZHOU, NING
Publication of US20210180158A1 publication Critical patent/US20210180158A1/en
Assigned to CRS HOLDINGS, LLC reassignment CRS HOLDINGS, LLC ENTITY CONVERSION Assignors: CRS HOLDINGS, INC.
Priority to US17/663,736 priority patent/US20220349032A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/0433Nickel- or cobalt-based alloys
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30Process control
    • B22F10/38Process control to achieve specific product aspects, e.g. surface smoothness, density, porosity or hollow structures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/60Treatment of workpieces or articles after build-up
    • B22F10/64Treatment of workpieces or articles after build-up by thermal means
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3033Ni as the principal constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00Materials specially adapted for additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00Products made by additive manufacturing
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/007Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056Alloys 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%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/057Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20Direct sintering or melting
    • B22F10/28Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30Process control
    • B22F10/36Process control of energy beam parameters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30Process control
    • B22F10/36Process control of energy beam parameters
    • B22F10/366Scanning parameters, e.g. hatch distance or scanning strategy
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00Working by laser beam, e.g. welding, cutting or boring
    • B23K26/34Laser welding for purposes other than joining
    • B23K26/342Build-up welding
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/25Process efficiency

Definitions

  • This invention relates generally to Ni-based superalloys and in particular to a Ni-based superalloy powder that is useful in an additive manufacturing process for making articles therefrom.
  • turbomachinery high temperature gas turbines and jet engines
  • a powder bed fusion technique using selective laser melting is one of the most promising additive manufacturing techniques. Compared with the known electron beam powder bed process, selective laser melting with powder bed does not require pre-sintering. Consequently, designers can incorporate complex internal features in the parts without worrying about removing sintered powder trapped inside hollows of the part after printing. Laser systems also offer finer resolution for printing intricate features.
  • the drawback of laser melting system is the large temperature gradient that occurs in a part during solidification.
  • the very large temperature gradient leads to cracking of the alloy, especially for superalloys having a high volume fraction of the gamma prime ( ⁇ ′) phase that provides superior strength and creep resistance such as CM247LC and Rene142.
  • ⁇ ′ gamma prime
  • For selective laser melting process cracking occurs either during build or post-build heat treatment.
  • Efforts have been made by the superalloy research community to mitigate the cracking problem, but have focused primarily on adjusting laser parameters such as power and scanning speed. There have been few attempts to modify the chemistries of the known superalloys, such as described in US20180347014A1, because of the reluctance to deviate from the known and accepted alloy chemistry specifications.
  • the balance of the alloy is at least about 50% nickel and the usual impurities found in commercial grades of Ni-base superalloys intended for the same use and service.
  • the alloy is further characterized by the following relationships among the constituent elements of the alloy:
  • the Ni-base superalloy powder may be embodied with any of the following preferred alloy weight percent compositions.
  • the balance of the alloy is at least about 50% nickel and the usual impurities found in commercial grades of Ni-base superalloys intended for the same use and service.
  • the alloy is further characterized by the following relationships among the constituent elements of the alloy:
  • the foregoing tabulations are provided as a convenient summary and are not intended to restrict the lower and upper values of the ranges of the individual elements for use in combination with each other, or to restrict the ranges of the elements for use solely in combination with each other.
  • one or more of the ranges can be used with one or more of the other ranges for the remaining elements.
  • a minimum or maximum for an element of one range can be used with the minimum or maximum for the same element in another range, and vice versa.
  • the alloy according to the present invention may comprise, consist essentially of, or consist of the constituent elements described above and throughout this application.
  • the alloy according to the present invention is designed to address the following problems: the transformation strain associated with the precipitation of ⁇ ′ during cooling and the internal stress buildup that occurs during aging heat treatment. Those phenomena combined with the fast ⁇ ′ precipitation kinetics and the residual stress inherent in the additive manufacturing process make the known alloys prone to strain-age cracking defects. It is an objective of the present invention to modify the known alloy chemistry and thereby, to tune the lattice misfit and precipitation kinetics to provide a new alloy that is optimized for the selective laser additive manufacturing process and which is strain-age cracking resistant while retaining a high ⁇ ′ volume fraction for superior elevated temperature strength and creep resistance.
  • an article made from consolidated powder produced with any of the alloys described above is characterized by having more than about 35 volume percent (vol. %) of the ⁇ ′ phase in gamma ( ⁇ ) phase matrix when the article is in the age hardened condition.
  • the article is further characterized by a lattice misfit parameter ( ⁇ ) that is greater than about ⁇ 0.1% and preferably about ⁇ 0.05% to about +0.6% where the lattice misfit parameter is defined as:
  • the parameter ⁇ ⁇ ′ is the lattice constant for the ⁇ ′ precipitate and parameter ⁇ ⁇ is the lattice constant for the ⁇ matrix material.
  • the term “percent” or the symbol “%” means percent by weight or mass percent, unless otherwise specified.
  • the term “high ⁇ ′ volume fraction” means at least 35% by volume (volume % or vol. %) of the ⁇ ′ phase in gamma ( ⁇ ) phase matrix of the alloy when in the age hardened condition.
  • the term “high strength” means a yield strength higher than that provided by Alloy 718 when produced with an additive manufacturing process tested at a temperature beyond 1500° F. (816° C.).
  • the term “high creep resistance” means a creep strength higher than that provided by Alloy 718 produced with an additive manufacturing process tested at a temperature beyond 1500° F. (816° C.).
  • the term “aging” is used synonymously with “age hardening” and “precipitation hardening”.
  • the term “solvus” means the solvus temperature as that term is generally understood.
  • FIG. 1A is a backscatter SEM image of an aged sample of Example 1 of the alloy according to the present invention
  • FIG. 1B is a backscatter SEM image of an aged sample of Example 2 of the alloy according to the present invention.
  • FIG. 1C is a backscatter SEM image of an aged sample of Example 3 of the alloy according to the present invention.
  • FIG. 1D is a backscatter SEM image of an aged sample of the CM247LC alloy
  • FIG. 2 shows a graph of the calculated misfit parameter compared to actual measured values of the misfit parameter for Examples 1-3 and the CM247L alloy;
  • FIG. 3A is an optical micrographic image of a sample of Example 1 after exposure at 1600° F. (871° C.) for 1000 hours showing an oxide layer at the surface of the sample;
  • FIG. 3B is an optical micrographic image of a sample of Example 2 after exposure at 1600° F. (871° C.) for 1000 hours showing an oxide layer at the surface of the sample;
  • FIG. 3C is an optical micrographic image of a sample of Example 3 after exposure at 1600° F. (871° C.) for 1000 hours showing an oxide layer at the surface of the sample;
  • FIG. 4A is an optical micrographic image of a sample of Example 1 of the alloy according to the present invention showing a resolidified melt pool after laser melting of the metal;
  • FIG. 4B is an optical micrographic image of a sample of Example 2 of the alloy according to the present invention showing a resolidified melt pool after laser melting of the metal;
  • FIG. 4C is an optical micrographic image of a sample of Example 3 of the alloy according to the present invention showing a resolidified melt pool after laser melting of the metal;
  • FIG. 4D is an optical micrographic image of a sample of the CM247LC alloy showing a resolidified melt pool after laser melting of the metal;
  • FIG. 5A is an optical micrographic image of a sample of Example 1 of the alloy according to this invention after laser melting and an aging heat treatment;
  • FIG. 5B is an optical micrographic image of a sample of Example 2 of the alloy according to this invention after laser melting and an aging heat treatment;
  • FIG. 5C is an optical micrographic image of a sample of Example 3 of the alloy according to this invention after laser melting and an aging heat treatment;
  • FIG. 5D is an optical micrographic image of a sample of the CM247LC alloy after laser melting and an aging heat treatment
  • FIG. 6A is a series of optical micrographic images of samples from builds of CM247LC alloy powder prepared with a laser powder bed fusion system at various laser power densities and various hatch spacings;
  • FIG. 6B is a series of optical micrographic images of samples from builds of alloy powder made from Example 1 and prepared with the laser powder bed fusion system at various laser power densities and various hatch spacings;
  • FIG. 6C is a series of optical micrographic images of samples from builds of alloy powder made from Example 2 and prepared with the laser powder bed fusion system at various laser power densities and various hatch spacings;
  • FIG. 7A is an optical micrographic image of one sample of the as-built CM247LC alloy after solution and aging heat treatments
  • FIG. 7B is an optical micrographic image of one sample of the as-built alloy of Example 1 after solution and aging heat treatments
  • FIG. 7C is an optical micrographic image of one sample of the as-built alloy of Example 2 after solution and aging heat treatments
  • FIG. 8 shows graphs of the tensile and yield strengths of Example 4 and Example 5 as a function of temperature in the range from room temperature to 1800° F. (982° C.);
  • FIG. 9 shows graphs representing the stress rupture lives of Example 4 and Example 5 based on the Larson-Miller parameter.
  • FIG. 10 shows graphs of the results of the 1800° F. (982° C.) cyclic oxidation testing of Example 4 and Example 5.
  • the alloy of this invention contains at least about 0.5% and preferably at least about 3% aluminum to combine with available nickel to form the ⁇ ′ phase, Ni 3 (Al,Ti), during cooling after laser melting and during subsequent aging of the alloy in consolidated form.
  • the alloy contains not more than about 5.5% and preferably not more than about 5% aluminum in order to benefit the weldability of the alloy. Up to about 2% titanium can be substituted for some of the aluminum for similar reasons.
  • the alloy contains not more than about 1% and for some applications not more than about 0.5% titanium.
  • the combined amount of Ti and Al should not be more than about 6%.
  • the alloy may contain about 3% to 6% and better yet, about 3.5% to 5% of aluminum and titanium combined (Al+Ti).
  • This alloy also contains at least about 7.5% tantalum. However, in a preferred embodiment the alloy may contain at least about 8.5% tantalum. Tantalum also combines with nickel to form the ⁇ ′ phase during cooling after laser melting and during subsequent aging of the alloy in consolidated form. Too much tantalum can lead to the formation of undesirable phases such as eta phase and delta phase. Therefore, tantalum is restricted to not more than about 10.5% and preferably to not more than about 9.5%. In a different embodiment, the alloy contains about 9.5% to about 11.5% tantalum. Up to about 6% niobium and up to about 2.0% hafnium may be present in this alloy in substitution for some of the tantalum for the same purpose. Tantalum, and niobium and hafnium when present, ensure that a sufficient volume of the ⁇ ′ phase is formed during the aging heat treatment of the additively manufactured product.
  • the alloy may optionally contain up to about 6% molybdenum, up to about 8% tungsten, up to about 6% rhenium, and up to about 3% ruthenium. Those elements tend to partition to the matrix material and their concentrations are controlled to shift the lattice misfit parameter toward a more positive value. A more positive lattice misfit parameter is believed to mitigate strain-age cracking that could otherwise occur in the alloy during solidification and subsequent aging heat treatment.
  • molybdenum is preferably limited to not more than about 5%
  • rhenium is limited to not more than about 5%
  • ruthenium is limited to not more than about 1%.
  • molybdenum is limited to not more than about 1.5%
  • tungsten is limited to not more than about 2%
  • rhenium is limited to not more than about 1%.
  • the combined amounts of molybdenum, tungsten, rhenium, and ruthenium are controlled such that % Mo+% W+% Re+% Rh is less than 12%, preferably about 2% to about 12%, and better yet about 3% to about 10%.
  • This alloy may contain up to about 15% cobalt or up to about 11% cobalt. Cobalt lowers the stacking fault energy in the crystal lattice and benefits the creep resistance property provided by the alloy. Cobalt also contributes to the corrosion resistance provided by the alloy. Toward those ends, a preferred embodiment of the alloy contains at least about 0.5% cobalt. A second preferred embodiment contains at least about 4% cobalt. A further embodiment contains at least about 9% cobalt. Too much cobalt can result in the precipitation of undesired phases such as sigma phase (Co—Cr). Therefore, the alloy preferably contains not more than about 10% cobalt. In one preferred embodiment the alloy contains not more than about 6% cobalt. In another preferred embodiment the alloy contains not more than about 2% cobalt. In a further embodiment, the alloy contains not more than about 1% cobalt.
  • the elements carbon, silicon, zirconium, and boron may be present in this alloy. However, those elements tend to depress the solidus temperature of the alloy and can segregate to the grain boundaries of the alloy matrix. In order to avoid or limit cracking on solidification, a narrow solidification temperature range is preferred. For these reasons in the present alloy carbon is restricted to not more than about 0.1%, silicon is restricted to not more than about 0.03%, zirconium is limited to not more than about 0.1%, and boron is limited to not more than about 0.03%. In the alloy of this invention, the combined amount of the elements C, Si, Zr, and B is not more than about 0.15% and preferably, not more than about 0.1%.
  • iron Up to about 1.5% iron may be present in the alloy of this invention. However, too much iron adversely affects the microstructural stability of the alloy and can combine with other elements to form undesired secondary phases such as sigma phase (Fe—Cr) and laves phase (e.g., Fe 2 Nb, Fe 2 Ti, and Fe 2 Mo). Therefore, the amount of iron is preferably restricted to not more than about 1.0%. Although it is not intentionally added, up to about 0.5% manganese may be present in this alloy as a residual from alloying additions during melting.
  • Fe—Cr sigma phase
  • laves phase e.g., Fe 2 Nb, Fe 2 Ti, and Fe 2 Mo
  • the balance of the alloy is at least about 50% nickel. Preferably, the alloy contains about 50-75% nickel.
  • the balance may also include minor amounts of inevitable impurity elements, such as phosphorus, sulfur, oxygen, and nitrogen, for example, not more than about 0.03% phosphorus and not more than about 0.01% each of sulfur oxygen and nitrogen.
  • the alloy according to this invention is preferably provided in powder form. Toward that end the alloy is vacuum induction melted and then atomized to form fine powder. The resulting powder is then screened to appropriate size for the additive manufacturing process.
  • Useful articles are prepared using any known technique for metal powder consolidation, for example, selective laser powder bed fusion. After the article is fully formed, it is preferably processed using different combinations and variations of hot isostatic pressing (HIP), solution heat treatment, quenching, and age hardening to develop the desired microstructure and properties.
  • Useful articles such as gas turbine components (e.g., turbine blades) can also be made by direct casting of the alloy using such casting techniques as directional solidification, equiaxed grain casting, and single crystal investment casting.
  • Examples 1, 2, and 3 were melted under vacuum and cast into ingots which were given a homogenization heat treatment after solidification.
  • Examples 1 and 2 were solution heat treated at 2250° F. (1232° C.) for one hour and quenched in water.
  • Example 3 was gas quenched from the homogenization temperature in a chamber backfilled with 10 bar of nitrogen.
  • the CM247LC example was melted under vacuum, homogenized after solidification, solution treated at 2250° F. (1232° C.) for one hour and quenched in water. After quenching, specimens of each alloy were aged at 1975° F. (1079° C.) for 4 hours followed by air cooling. The specimens were then heat treated with a second aging at 1600° F. (871° C.) for 20 hours and then air cooled.
  • the microstructures of Examples 1-3 after aging are shown in FIGS. 1A-1C , respectively.
  • the microstructure of an aged specimen of the CM247LC example is shown in FIG. 1D for comparison.
  • the volume percent of ⁇ ′ in Examples 1-3 after aging is about 60 vol. % based on image analysis.
  • the volume fraction of ⁇ ′ in Example 3 after aging is slightly higher than that of ⁇ ′ in Examples 1 and 2.
  • the equivalent diameter of the ⁇ ′ precipitates in all 3 examples after ageing is about 300 to 500 nm.
  • the lattice misfit parameters ( 6 ) of Examples 1-3 and CM247LC were calculated using the THERMO-CALC software for a temperature of 1600° F. (871° C.). Actual lattice misfit parameters for Examples 1-3 and CM247LC were measured by x-ray diffraction (XRD). The calculated and measured values of 6 for each example are shown in Table 2 below.
  • FIGS. 3A-3C Shown in FIGS. 3A-3C are optical images of specimens of Examples 1-3 after being solution treated, aged, and then heated for 1000 h at 1600° F. (871° C.). It can be seen that a continuous external oxide layer forms on the alloy surface. All three of the examples are microstructurally stable without formation of detrimental phases during exposure.
  • FIGS. 4A-4D show the melt pool structures in the alloy specimens after a bead-on-plate test (the external surface is facing downward in the figure).
  • the sample of CM247LC ( FIG. 4D ) has cracks in the melt pool while the Examples 1-3 ( FIGS. 4A, 4B, and 4C , respectively) are free of cracks with all the power density and hatch-spacing combinations tested.
  • FIGS. 5A-5D The results are shown in FIGS. 5A-5D .
  • the aging heat treatment eliminated the dendritic structure in the as-built condition and made it difficult to discern the melt pool location.
  • alloy CM247LC FIG. 5D
  • FIGS. 5A, 5B, and 5C show no sign of cracks and which demonstrates that they are highly resistant to strain-age cracking.
  • FIG. 6A shows the as-built microstructures of the CM247LC samples have severe cracking issues for most test conditions.
  • FIG. 6B shows the as-built microstructures of Example 1 and
  • FIG. 6C shows the as-built microstructures of Example 2.
  • FIGS. 6B and 6C show good crack resistance and demonstrate that the Examples 1 and 2 provide a large processing window in which to achieve good build quality with very low porosity and very low crack density.
  • FIG. 7A shows a substantial number of thin hairline cracks in the CM247LC material after aging
  • FIG. 7B and FIG. 7C show that the material of Example 1 and Example 2 remain crack free after post build heat treatment.
  • Additional examples were prepared by Argon gas atomization having the weight percent compositions shown in Table 3 below.
  • the batches of alloy powder were consolidated and then processed to provide standard specimens for tensile and stress rupture testing.
  • Cyclic oxidation testing was performed on specimens of Examples 4 and 5.
  • the cyclic oxidation test was performed at 1800° F. (982° C.), with each cycle made up of 0.25 hr ramping, a 1-hour hold at 1800° F. (982° C.), and 0.25 hr forced air cool.
  • the results of the cyclic oxidation testing are set forth in Table 5 below including the number of cycles and the specific weight change in g/cm 2 .
  • Example 5 0 0 0 10 3.813(10 ⁇ 5 ) 3.472(10 ⁇ 4 ) 20 2.288(10 ⁇ 4) 4.244(10 ⁇ 4 ) 50 7.626(10 ⁇ 5 ) 7.716(10 ⁇ 4 ) 100 3.051(10 ⁇ 4 ) 8.488(10 ⁇ 4 ) 150 4.004(10 ⁇ 4 ) 1.138(10 ⁇ 3 ) 200 5.148(10 ⁇ 4 ) 1.119(10 ⁇ 3 ) 300 4.004(10 ⁇ 4 ) 1.196(10 ⁇ 3 ) 400 2.097(10 ⁇ 4 ) 1.389(10 ⁇ 3 ) 600 1.716(10 ⁇ 4 ) 1.447(10 ⁇ 3 ) 800 4.004(10 ⁇ 4 ) 1.678(10 ⁇ 3 ) 1000 3.813(10 ⁇ 5 ) 3.472(10 ⁇ 4 )
  • FIG. 10 shows graphs of the data presented in Table 4. Both Example 4 and Example 5 appear to be oxidation resistant since they did not experience weight loss up to 1000 cycles.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Automation & Control Theory (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Powder Metallurgy (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Abstract

A nickel base superalloy powder for additive manufacturing applications is disclosed. The alloy powder has the following broad weight percent composition:C 0-0.1Mn0.5 max.Si  0-0.03Cr 4-16Fe 0-1.5Mo0-6W0-8Co 0-15Ti0-2Al0.5-5.5Nb0-6Ta 7.5-14.5Hf 0-2.0Zr 0-0.1Re0-6Ru0-3B  0-0.03The balance of the alloy is at least 50% nickel and the usual impurities. An article of manufacture made from the alloy is also disclosed.

Description

    CROSS REFERENCE TO RELATED APPLICATION
  • This application claims the benefit of U.S. Provisional Patent Application No. 62/795,618, filed Jan. 23, 2019, the entirety of which is incorporated herein by reference.
  • BACKGROUND OF THE INVENTION Field of the Invention
  • This invention relates generally to Ni-based superalloys and in particular to a Ni-based superalloy powder that is useful in an additive manufacturing process for making articles therefrom.
  • Description of the Related Art
  • With the advent of additive manufacturing technologies, manufacturers of turbomachinery (high temperature gas turbines and jet engines) are looking at leveraging the design flexibility offered by the additive manufacturing process to directly produce parts with complex features for use in the hot gas path of gas turbines and jet engines. A powder bed fusion technique using selective laser melting is one of the most promising additive manufacturing techniques. Compared with the known electron beam powder bed process, selective laser melting with powder bed does not require pre-sintering. Consequently, designers can incorporate complex internal features in the parts without worrying about removing sintered powder trapped inside hollows of the part after printing. Laser systems also offer finer resolution for printing intricate features.
  • The drawback of laser melting system is the large temperature gradient that occurs in a part during solidification. The very large temperature gradient leads to cracking of the alloy, especially for superalloys having a high volume fraction of the gamma prime (γ′) phase that provides superior strength and creep resistance such as CM247LC and Rene142. For selective laser melting process, cracking occurs either during build or post-build heat treatment. Efforts have been made by the superalloy research community to mitigate the cracking problem, but have focused primarily on adjusting laser parameters such as power and scanning speed. There have been few attempts to modify the chemistries of the known superalloys, such as described in US20180347014A1, because of the reluctance to deviate from the known and accepted alloy chemistry specifications.
  • SUMMARY OF THE INVENTION
  • The problems associated with the known superalloys as discussed above are resolved to a large degree by an alloy powder having the following broad and intermediate weight percent ranges.
  • Element Broad Intermediate
    C 0-0.1 0-0.1
    Mn 0.5 max. 0.5 max.
    Si   0-0.03   0-0.03
    Cr  4-16  4-11
    Fe 0-1.5 0-1
    Mo 0-6 0-5
    W 0-8 0.5-8
    Co  0-15  0-10
    Ti 0-2 0-1
    Al 0.5-5.5 3-5
    Nb 0-6 0-5
    Ta  7.5-14.5  7.5-11.5
    Hf 0-2.0 0-1.5
    Zr 0-0.1 0-0.1
    Re 0-6 0-5
    Ru 0-3 0-3
    B   0-0.03   0-0.03
  • The balance of the alloy is at least about 50% nickel and the usual impurities found in commercial grades of Ni-base superalloys intended for the same use and service. The alloy is further characterized by the following relationships among the constituent elements of the alloy:
      • % Al+% Ti≤6;
      • % W+% Mo+% Ru+% Re<10; and
      • % C+% B+% Si+% Zr<0.15.
  • In accordance with another aspect of the present invention, the Ni-base superalloy powder may be embodied with any of the following preferred alloy weight percent compositions.
  • Pre- Pre- Pre- Pre- Pre-
    ferred ferred ferred ferred ferred
    Element A B C D E
    C 0-0.1 0-0.1 0-0.1 0-0.1 0-0.1
    Mn 0.5 max.   0.5 max.   0.5 max.   0.5 max.   0.5 max.  
    Si   0-0.03   0-0.03   0-0.03   0-0.03  0-0.03
    Cr  9-11  9-11 4-8  9-11 8-10 
    Fe 1 max. 1 max. 1 max. 1 max. 1 max
    Mo 2-5 2-5 0.5-1.5 2-5 2-5
    W 0.5-2 0.5-2 6-8 3.5-4.5 4-6
    Co 4-6 0.5-2 0-1 0.5-2 9-11 
    Ti 0-0.5 0-0.5 0-1 0-0.5 0-0.5
    Al 3-5 3-5 3-5 3-5 4-5.5
    Nb 3-5 2.5-4 0-1 2.5-4 0-1
    Ta 7.5-9.5  8.5-10.5  8.5-10.5  8.5-10.5 9.5-11.5 
    Hf 0-0.5 0-0.5 0.5-1.5 0-0.5 0-0.5
    Zr 0-0.1 0-0.1 0-0.1 0-0.1 0-0.1
    Re 0-1 0-1 0-1 0-1 0-1
    Ru 0-1 0-1 0-1 0-1 0-1
    B   0-0.03   0-0.03   0-0.03   0-0.03  0-0.03
  • The balance of the alloy is at least about 50% nickel and the usual impurities found in commercial grades of Ni-base superalloys intended for the same use and service. The alloy is further characterized by the following relationships among the constituent elements of the alloy:
      • % Al+% Ti≤6;
      • % W+% Mo+% Ru+% Re<10; and
      • % C+% B+% Si+% Zr<0.1.
  • The foregoing tabulations are provided as a convenient summary and are not intended to restrict the lower and upper values of the ranges of the individual elements for use in combination with each other, or to restrict the ranges of the elements for use solely in combination with each other. Thus, one or more of the ranges can be used with one or more of the other ranges for the remaining elements. In addition, a minimum or maximum for an element of one range can be used with the minimum or maximum for the same element in another range, and vice versa. Moreover, the alloy according to the present invention may comprise, consist essentially of, or consist of the constituent elements described above and throughout this application.
  • The alloy according to the present invention is designed to address the following problems: the transformation strain associated with the precipitation of γ′ during cooling and the internal stress buildup that occurs during aging heat treatment. Those phenomena combined with the fast γ′ precipitation kinetics and the residual stress inherent in the additive manufacturing process make the known alloys prone to strain-age cracking defects. It is an objective of the present invention to modify the known alloy chemistry and thereby, to tune the lattice misfit and precipitation kinetics to provide a new alloy that is optimized for the selective laser additive manufacturing process and which is strain-age cracking resistant while retaining a high γ′ volume fraction for superior elevated temperature strength and creep resistance.
  • In accordance with another aspect of the present invention there is provided an article made from consolidated powder produced with any of the alloys described above. The article is characterized by having more than about 35 volume percent (vol. %) of the γ′ phase in gamma (γ) phase matrix when the article is in the age hardened condition. The article is further characterized by a lattice misfit parameter (δ) that is greater than about −0.1% and preferably about −0.05% to about +0.6% where the lattice misfit parameter is defined as:
  • δ = 2 × ( α γ - α γ ) α γ + α γ
  • The parameter αγ′ is the lattice constant for the γ′ precipitate and parameter αγ is the lattice constant for the γ matrix material.
  • Here and throughout this specification the term “percent” or the symbol “%” means percent by weight or mass percent, unless otherwise specified. The term “high γ′ volume fraction” means at least 35% by volume (volume % or vol. %) of the γ′ phase in gamma (γ) phase matrix of the alloy when in the age hardened condition. The term “high strength” means a yield strength higher than that provided by Alloy 718 when produced with an additive manufacturing process tested at a temperature beyond 1500° F. (816° C.). The term “high creep resistance” means a creep strength higher than that provided by Alloy 718 produced with an additive manufacturing process tested at a temperature beyond 1500° F. (816° C.). The term “aging” is used synonymously with “age hardening” and “precipitation hardening”. Moreover, the term “solvus” means the solvus temperature as that term is generally understood.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • The working examples described in the following detailed description of the invention will be better understood when read with reference to the drawings wherein:
  • FIG. 1A is a backscatter SEM image of an aged sample of Example 1 of the alloy according to the present invention;
  • FIG. 1B is a backscatter SEM image of an aged sample of Example 2 of the alloy according to the present invention;
  • FIG. 1C is a backscatter SEM image of an aged sample of Example 3 of the alloy according to the present invention;
  • FIG. 1D is a backscatter SEM image of an aged sample of the CM247LC alloy;
  • FIG. 2 shows a graph of the calculated misfit parameter compared to actual measured values of the misfit parameter for Examples 1-3 and the CM247L alloy;
  • FIG. 3A is an optical micrographic image of a sample of Example 1 after exposure at 1600° F. (871° C.) for 1000 hours showing an oxide layer at the surface of the sample;
  • FIG. 3B is an optical micrographic image of a sample of Example 2 after exposure at 1600° F. (871° C.) for 1000 hours showing an oxide layer at the surface of the sample;
  • FIG. 3C is an optical micrographic image of a sample of Example 3 after exposure at 1600° F. (871° C.) for 1000 hours showing an oxide layer at the surface of the sample;
  • FIG. 4A is an optical micrographic image of a sample of Example 1 of the alloy according to the present invention showing a resolidified melt pool after laser melting of the metal;
  • FIG. 4B is an optical micrographic image of a sample of Example 2 of the alloy according to the present invention showing a resolidified melt pool after laser melting of the metal;
  • FIG. 4C is an optical micrographic image of a sample of Example 3 of the alloy according to the present invention showing a resolidified melt pool after laser melting of the metal;
  • FIG. 4D is an optical micrographic image of a sample of the CM247LC alloy showing a resolidified melt pool after laser melting of the metal;
  • FIG. 5A is an optical micrographic image of a sample of Example 1 of the alloy according to this invention after laser melting and an aging heat treatment;
  • FIG. 5B is an optical micrographic image of a sample of Example 2 of the alloy according to this invention after laser melting and an aging heat treatment;
  • FIG. 5C is an optical micrographic image of a sample of Example 3 of the alloy according to this invention after laser melting and an aging heat treatment;
  • FIG. 5D is an optical micrographic image of a sample of the CM247LC alloy after laser melting and an aging heat treatment;
  • FIG. 6A is a series of optical micrographic images of samples from builds of CM247LC alloy powder prepared with a laser powder bed fusion system at various laser power densities and various hatch spacings;
  • FIG. 6B is a series of optical micrographic images of samples from builds of alloy powder made from Example 1 and prepared with the laser powder bed fusion system at various laser power densities and various hatch spacings;
  • FIG. 6C is a series of optical micrographic images of samples from builds of alloy powder made from Example 2 and prepared with the laser powder bed fusion system at various laser power densities and various hatch spacings;
  • FIG. 7A is an optical micrographic image of one sample of the as-built CM247LC alloy after solution and aging heat treatments;
  • FIG. 7B is an optical micrographic image of one sample of the as-built alloy of Example 1 after solution and aging heat treatments;
  • FIG. 7C is an optical micrographic image of one sample of the as-built alloy of Example 2 after solution and aging heat treatments;
  • FIG. 8 shows graphs of the tensile and yield strengths of Example 4 and Example 5 as a function of temperature in the range from room temperature to 1800° F. (982° C.);
  • FIG. 9 shows graphs representing the stress rupture lives of Example 4 and Example 5 based on the Larson-Miller parameter; and
  • FIG. 10 shows graphs of the results of the 1800° F. (982° C.) cyclic oxidation testing of Example 4 and Example 5.
  • DETAILED DESCRIPTION
  • The alloy of this invention contains at least about 0.5% and preferably at least about 3% aluminum to combine with available nickel to form the γ′ phase, Ni3(Al,Ti), during cooling after laser melting and during subsequent aging of the alloy in consolidated form. The alloy contains not more than about 5.5% and preferably not more than about 5% aluminum in order to benefit the weldability of the alloy. Up to about 2% titanium can be substituted for some of the aluminum for similar reasons. Preferably, the alloy contains not more than about 1% and for some applications not more than about 0.5% titanium. The combined amount of Ti and Al should not be more than about 6%. Preferably, the alloy may contain about 3% to 6% and better yet, about 3.5% to 5% of aluminum and titanium combined (Al+Ti).
  • This alloy also contains at least about 7.5% tantalum. However, in a preferred embodiment the alloy may contain at least about 8.5% tantalum. Tantalum also combines with nickel to form the γ′ phase during cooling after laser melting and during subsequent aging of the alloy in consolidated form. Too much tantalum can lead to the formation of undesirable phases such as eta phase and delta phase. Therefore, tantalum is restricted to not more than about 10.5% and preferably to not more than about 9.5%. In a different embodiment, the alloy contains about 9.5% to about 11.5% tantalum. Up to about 6% niobium and up to about 2.0% hafnium may be present in this alloy in substitution for some of the tantalum for the same purpose. Tantalum, and niobium and hafnium when present, ensure that a sufficient volume of the γ′ phase is formed during the aging heat treatment of the additively manufactured product.
  • The alloy may optionally contain up to about 6% molybdenum, up to about 8% tungsten, up to about 6% rhenium, and up to about 3% ruthenium. Those elements tend to partition to the matrix material and their concentrations are controlled to shift the lattice misfit parameter toward a more positive value. A more positive lattice misfit parameter is believed to mitigate strain-age cracking that could otherwise occur in the alloy during solidification and subsequent aging heat treatment. When present, molybdenum is preferably limited to not more than about 5%, rhenium is limited to not more than about 5%, ruthenium is limited to not more than about 1%. For certain applications molybdenum is limited to not more than about 1.5%, tungsten is limited to not more than about 2%, and rhenium is limited to not more than about 1%. When present in this alloy, the combined amounts of molybdenum, tungsten, rhenium, and ruthenium are controlled such that % Mo+% W+% Re+% Rh is less than 12%, preferably about 2% to about 12%, and better yet about 3% to about 10%.
  • This alloy may contain up to about 15% cobalt or up to about 11% cobalt. Cobalt lowers the stacking fault energy in the crystal lattice and benefits the creep resistance property provided by the alloy. Cobalt also contributes to the corrosion resistance provided by the alloy. Toward those ends, a preferred embodiment of the alloy contains at least about 0.5% cobalt. A second preferred embodiment contains at least about 4% cobalt. A further embodiment contains at least about 9% cobalt. Too much cobalt can result in the precipitation of undesired phases such as sigma phase (Co—Cr). Therefore, the alloy preferably contains not more than about 10% cobalt. In one preferred embodiment the alloy contains not more than about 6% cobalt. In another preferred embodiment the alloy contains not more than about 2% cobalt. In a further embodiment, the alloy contains not more than about 1% cobalt.
  • The elements carbon, silicon, zirconium, and boron may be present in this alloy. However, those elements tend to depress the solidus temperature of the alloy and can segregate to the grain boundaries of the alloy matrix. In order to avoid or limit cracking on solidification, a narrow solidification temperature range is preferred. For these reasons in the present alloy carbon is restricted to not more than about 0.1%, silicon is restricted to not more than about 0.03%, zirconium is limited to not more than about 0.1%, and boron is limited to not more than about 0.03%. In the alloy of this invention, the combined amount of the elements C, Si, Zr, and B is not more than about 0.15% and preferably, not more than about 0.1%.
  • Up to about 1.5% iron may be present in the alloy of this invention. However, too much iron adversely affects the microstructural stability of the alloy and can combine with other elements to form undesired secondary phases such as sigma phase (Fe—Cr) and laves phase (e.g., Fe2Nb, Fe2Ti, and Fe2Mo). Therefore, the amount of iron is preferably restricted to not more than about 1.0%. Although it is not intentionally added, up to about 0.5% manganese may be present in this alloy as a residual from alloying additions during melting.
  • The balance of the alloy is at least about 50% nickel. Preferably, the alloy contains about 50-75% nickel. The balance may also include minor amounts of inevitable impurity elements, such as phosphorus, sulfur, oxygen, and nitrogen, for example, not more than about 0.03% phosphorus and not more than about 0.01% each of sulfur oxygen and nitrogen.
  • The alloy according to this invention is preferably provided in powder form. Toward that end the alloy is vacuum induction melted and then atomized to form fine powder. The resulting powder is then screened to appropriate size for the additive manufacturing process. Useful articles are prepared using any known technique for metal powder consolidation, for example, selective laser powder bed fusion. After the article is fully formed, it is preferably processed using different combinations and variations of hot isostatic pressing (HIP), solution heat treatment, quenching, and age hardening to develop the desired microstructure and properties. Useful articles such as gas turbine components (e.g., turbine blades) can also be made by direct casting of the alloy using such casting techniques as directional solidification, equiaxed grain casting, and single crystal investment casting.
  • WORKING EXAMPLES
  • In order to demonstrate the desirable combination of properties provided by the alloy of this invention, a set of comparative examples were melted, processed, and tested. Set forth in Table 1 below are the weight percent compositions of four heats that were melted and tested.
  • TABLE 1
    Al Co Cr Hf Mo Nb Ta Ti W Ni
    Example 1  4.05 5.01  9.79 0    2.96 3.86 7.93 0   0.86 Bal1
    Example 2  4.09 1.62  9.78 0    2.96 3.07 9.36 0   0.75 Bal1
    Example 3  3.95 0.11 5.8 1.18  0.99 0   9.37 0.52 7.37 Bal1
    CM247LC2 5.6 9.27 8.2 1.39 0.6 3.29 0.64 9.21 61.65
    1Balance includes usual impurity elements.
    2Also includes 0.03% Zr, 0.014% B, and 0.082% C.
  • Examples 1, 2, and 3 were melted under vacuum and cast into ingots which were given a homogenization heat treatment after solidification. Examples 1 and 2 were solution heat treated at 2250° F. (1232° C.) for one hour and quenched in water. Example 3 was gas quenched from the homogenization temperature in a chamber backfilled with 10 bar of nitrogen. The CM247LC example was melted under vacuum, homogenized after solidification, solution treated at 2250° F. (1232° C.) for one hour and quenched in water. After quenching, specimens of each alloy were aged at 1975° F. (1079° C.) for 4 hours followed by air cooling. The specimens were then heat treated with a second aging at 1600° F. (871° C.) for 20 hours and then air cooled.
  • The microstructures of Examples 1-3 after aging are shown in FIGS. 1A-1C, respectively. The microstructure of an aged specimen of the CM247LC example is shown in FIG. 1D for comparison. The volume percent of γ′ in Examples 1-3 after aging is about 60 vol. % based on image analysis. The volume fraction of γ′ in Example 3 after aging is slightly higher than that of γ′ in Examples 1 and 2. The equivalent diameter of the γ′ precipitates in all 3 examples after ageing is about 300 to 500 nm.
  • The lattice misfit parameters (6) of Examples 1-3 and CM247LC were calculated using the THERMO-CALC software for a temperature of 1600° F. (871° C.). Actual lattice misfit parameters for Examples 1-3 and CM247LC were measured by x-ray diffraction (XRD). The calculated and measured values of 6 for each example are shown in Table 2 below.
  • TABLE 2
    Example Calculated Lattice Misfit Measured Misfit
    1 0.09 0.209
    2 −0.02 0.055
    3 0.33 0.294
    CM247LC −0.152 −0.035

    The results presented in Table 2 are graphed in FIG. 2 to show the good correlation between the actual and calculated values.
  • Shown in FIGS. 3A-3C are optical images of specimens of Examples 1-3 after being solution treated, aged, and then heated for 1000 h at 1600° F. (871° C.). It can be seen that a continuous external oxide layer forms on the alloy surface. All three of the examples are microstructurally stable without formation of detrimental phases during exposure.
  • FIGS. 4A-4D show the melt pool structures in the alloy specimens after a bead-on-plate test (the external surface is facing downward in the figure). The sample of CM247LC (FIG. 4D) has cracks in the melt pool while the Examples 1-3 (FIGS. 4A, 4B, and 4C, respectively) are free of cracks with all the power density and hatch-spacing combinations tested.
  • Additional heat treatment was carried out on the examples after the bead-on-plate test. The heat treatment consisted of heating the examples at 1975° F. (1079° C.) for 4 hours, cooling in air, and then heating at 1600° F. (871° C.) for 20 hours, followed by cooling in air. In this procedure, a laser is used to produce a weld-bead track on a metal plate. The results are shown in FIGS. 5A-5D. The aging heat treatment eliminated the dendritic structure in the as-built condition and made it difficult to discern the melt pool location. Compared to alloy CM247LC (FIG. 5D), which showed strain-age cracking, the three examples of the alloy of the present invention (FIGS. 5A, 5B, and 5C) show no sign of cracks and which demonstrates that they are highly resistant to strain-age cracking.
  • Based on the results from the bead-on-plate test, batches of gas-atomized powder of the example alloys and the CM247LC alloy were produced. Additively manufactured samples were printed with a laser powder bed fusion system. The processing parameters (including laser power, scan speed, hatch spacing, etc.) were varied to provide a plurality of build samples. The as-built microstructures of the several samples are shown in FIGS. 6A to 6B. Each image was taken at 50× magnification. Thus, each image corresponds to a field of view about 2.6 mm by 2.2 mm. In FIGS. 6A-6C, the laser power density increases from left to right while the hatch spacing decreases from top to bottom. FIG. 6A shows the as-built microstructures of the CM247LC samples have severe cracking issues for most test conditions. FIG. 6B, shows the as-built microstructures of Example 1 and FIG. 6C shows the as-built microstructures of Example 2. FIGS. 6B and 6C show good crack resistance and demonstrate that the Examples 1 and 2 provide a large processing window in which to achieve good build quality with very low porosity and very low crack density.
  • Samples with the lowest crack density and porosity were selected from each alloy and further processed with a post-build heat treatment consisting of solution and aging heat treatments. The samples were solution treated at 2250° F. (1232° C.) for one hour, quenched in water, aged at 1975° F. (1079° C.) for 4 hours, air cooled, aged at 1600° F. (871° C.) for 20 hours, and then cooled in air. FIG. 7A shows a substantial number of thin hairline cracks in the CM247LC material after aging, while FIG. 7B and FIG. 7C show that the material of Example 1 and Example 2 remain crack free after post build heat treatment.
  • Additional examples were prepared by Argon gas atomization having the weight percent compositions shown in Table 3 below. The batches of alloy powder were consolidated and then processed to provide standard specimens for tensile and stress rupture testing.
  • TABLE 3
    Ex. Al Co Cr Mo Nb Ta W C B Zr Ni
    4 4.0 5.2 9.9 3.0 4.0 7.9 1.2 0.077 0.015 0.013 Bal
    5 4.1 1.6 9.7 3.0 3.1 8.9 3.8 0.038 0.007 0.010 Bal
  • Tensile testing was performed on the specimens of Examples 4 and 5 at several temperatures in the range from room temperature up to 1800° F. (982° C.). The results of the tensile testing are set forth in Table 4 below including the test temperature in degrees Celsius and the ultimate tensile strength and the yield strength in MPa. The results are also plotted in FIG. 8.
  • TABLE 4
    Temp. Example 4 Example 5
    (° C.) UTS(MPa) YS(MPa) UTS(MPa) YS(MPa)
    21 1413.4 979.1 1461.7 1054.9
    593 1285.9 865.3 1296.9 978.4
    760 946.7 903.9 1008.3 947.3
    871 523.3 522.6 530.6 477.8
    982 299.9 255.8 228.9
  • Stress rupture testing was performed on the specimens of Examples 4 and 5 at several temperatures in the range from 1300° F. to 1700° F. (704° C. to 927° C.). The results of the stress rupture testing are plotted in FIG. 9 based on the Larson-Miller parameter.
  • Cyclic oxidation testing was performed on specimens of Examples 4 and 5. The cyclic oxidation test was performed at 1800° F. (982° C.), with each cycle made up of 0.25 hr ramping, a 1-hour hold at 1800° F. (982° C.), and 0.25 hr forced air cool. The results of the cyclic oxidation testing are set forth in Table 5 below including the number of cycles and the specific weight change in g/cm2.
  • TABLE 5
    Specific Weight Change
    Cycles Example 4 Example 5
    0 0 0
    10 3.813(10−5) 3.472(10−4)
    20 2.288(10−4) 4.244(10−4)
    50 7.626(10−5) 7.716(10−4)
    100 3.051(10−4) 8.488(10−4)
    150 4.004(10−4) 1.138(10−3)
    200 5.148(10−4) 1.119(10−3)
    300 4.004(10−4) 1.196(10−3)
    400 2.097(10−4) 1.389(10−3)
    600 1.716(10−4) 1.447(10−3)
    800 4.004(10−4) 1.678(10−3)
    1000 3.813(10−5) 3.472(10−4)
  • FIG. 10 shows graphs of the data presented in Table 4. Both Example 4 and Example 5 appear to be oxidation resistant since they did not experience weight loss up to 1000 cycles.
  • The terms and expressions which are employed in this specification are used as terms of description and not of limitation. There is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof. It is recognized that various modifications are possible within the invention described and claimed herein.

Claims (19)

1. A high γ′ volume fraction Ni-base alloy optimized for laser and electron beam additive manufacturing processes with improved solidification and strain-age cracking resistance and high strength and creep resistance at elevated temperature, said alloy consisting essentially of, in weight percent, about
C 0-0.1 Mn 0.5 max. Si   0-0.03 Cr  4-16 Fe 1.5 max. Mo 0-6 W 0-8 Co  0-15 Ti 0-2 Al 0.5-5.5 Nb 0-6 Ta  7.5-14.5 Hf 0-2.0 Zr 0-0.1 Re 0-6 Ru 0-3 B   0-0.03
and the balance of the alloy is at least about 50% nickel and the usual impurities found in commercial grades of Ni-base superalloys intended for the same use and service.
2. The alloy claimed in claim 1 which contains, about
Cr  9-11 Fe 1 max. Mo 2-5 W 0.5-2 Co 4-6 Ti 0-0.5 Al 3-5 Nb 3-5 Ta 7.5-9.5 Hf 0-0.5 Re 0-1 Ru 0-1
and the balance of the alloy is at least about 50% nickel and usual impurities.
3. The alloy claimed in claim 1 which contains about
Cr  9-11 Fe 1 max. Mo 2-5 W 0.5-2 Co 0.5-2 Ti 0-0.5 Al 3-5 Nb 2.5-4 Ta  8.5-10.5 Hf 0-0.5 Re 0-1 Ru 0-1
and the balance of the alloy is at least about 50% nickel and usual impurities.
4. The alloy claimed in claim 1 which contains about
Cr 4-8 Fe 1 max. Mo 0.5-1.5 W 6-8 Co 0-1 Ti 0-1 Al 3-5 Nb 0-1 Ta  8.5-10.5 Hf 0.5-1.5 Re 0-1 Ru 0-1
and the balance of the alloy is at least about 50% nickel and usual impurities.
5. The alloy claimed in claim 1 which contains about
Cr  9-11 Fe 1 max. Mo 2-5 W 3.5-4.5 Co 0.5-2 Ti 0-0.5 Al 3-5 Nb 2.5-4 Ta  8.5-10.5 Hf 0-0.5 Re 0-1 Ru 0-1
and the balance of the alloy is at least about 50% nickel and usual impurities.
6. The alloy claimed in claim 1 which contains about:
Cr  8-10 Fe 1 max. Mo 2-5 W 4-6 Co  9-11 Ti 0-0.5 Al 4-5.5 Nb 0-1 Ta  9.5-11.5 Hf 0-0.5 Re 0-1 Ru 0-1
and the balance of the alloy is at least about 50% nickel and the usual impurities.
7. The alloy claimed in claim 1 wherein Al+Ti is about 3 to about 6 weight percent and W+Mo+Ru+Re is about 2 to about 12 weight percent.
8. The alloy claimed in claim 7 wherein C+B+Si+Zr is less than about 0.15 weight percent for reducing solidification range and improving solidification cracking resistance.
9. A high γ′ volume fraction Ni-base alloy optimized for laser and electron beam additive manufacturing processes with improved solidification and strain-age cracking resistance and high strength and creep resistance at elevated temperature, said alloy consisting essentially of, in weight percent, about
C 0-0.1 Mn 0.5 max.   Si   0-0.03 Cr  4-11 Fe 1 max. Mo 0-5 W 0.5-8 Co  0-10 Ti 0-1 Al 3-5 Nb 0-5 Ta  7.5-11.5 Hf 0-1.5 Zr 0-0.1 Re 0-5 Ru 0-3 B   0-0.03
and the balance of the alloy is at least about 50% nickel and the usual impurities found in commercial grades of Ni-base superalloys intended for the same use and service.
10. The alloy claimed in claim 9 which contains, about
Cr  9-11 Fe 1 max. Mo 2-5 W 0.5-2 Co 4-6 Ti 0-0.5 Al 3-5 Nb 3-5 Ta 7.5-9.5 Hf 0-0.5 Re 0-1 Ru 0-1
and the balance of the alloy is at least about 50% nickel and usual impurities.
11. The alloy claimed in claim 9 which contains about
Cr  9-11 Fe 1 max. Mo 2-5 W 0.5-2 Co 0.5-2 Ti 0-0.5 Al 3-5 Nb 2.5-4 Ta  8.5-10.5 Hf 0-0.5 Re 0-1 Ru 0-1
and the balance of the alloy is at least about 50% nickel and usual impurities.
12. The alloy claimed in claim 9 which contains about
Cr 4-8 Fe 1 max. Mo 0.5-1.5 W 6-8 Co 0-1 Ti 0-1 Al 3-5 Nb 0-1 Ta  8.5-10.5 Hf 0.5-1.5 Re 0-1 Ru 0-1
and the balance of the alloy is at least about 50% nickel and usual impurities.
13. The alloy claimed in claim 9 which contains about:
Cr  9-11 Fe 1 max. Mo 2-5 W 3.5-4.5 Co 0.5-2 Ti 0-0.5 Al 3-5 Nb 2.5-4 Ta  8.5-10.5 Hf 0-0.5 Re 0-1 Ru 0-1
and the balance of the alloy is at least about 50% nickel and usual impurities.
14. The alloy claimed in claim 9 wherein Al+Ti is about 3.5 to about 5.5 weight percent and W+Mo+Ru+Re is about 3 to about 10 weight percent.
15. The alloy claimed in claim 14 wherein C+B+Si+Zr is less than about 0.10 weight percent for reducing solidification range and improving solidification cracking resistance.
16. The alloy claimed in claim 1 or claim 9 comprising a γ′ strengthening phase.
17. The alloy claimed in claim 16 wherein the γ′ phase has a volume fraction that is greater than 35%.
18. The alloy claimed in claim 17 wherein the γ′ phase has a volume fraction that is greater than 50%.
19. The alloy claimed in claim 1 or claim 9 which has a γ′ solvus temperature 7 higher than 2050° F. (1121° C.).
US16/750,745 2019-01-23 2020-01-23 Ni-Based Superalloy Powder for Additive Manufacturing and an Article Made Therefrom Abandoned US20210180158A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US16/750,745 US20210180158A1 (en) 2019-01-23 2020-01-23 Ni-Based Superalloy Powder for Additive Manufacturing and an Article Made Therefrom
US17/663,736 US20220349032A1 (en) 2019-01-23 2022-05-17 Ni-Based Superalloy Powder for Additive Manufacturing and an Article Made Therefrom

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201962795618P 2019-01-23 2019-01-23
US16/750,745 US20210180158A1 (en) 2019-01-23 2020-01-23 Ni-Based Superalloy Powder for Additive Manufacturing and an Article Made Therefrom

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US17/663,736 Continuation US20220349032A1 (en) 2019-01-23 2022-05-17 Ni-Based Superalloy Powder for Additive Manufacturing and an Article Made Therefrom

Publications (1)

Publication Number Publication Date
US20210180158A1 true US20210180158A1 (en) 2021-06-17

Family

ID=69780282

Family Applications (2)

Application Number Title Priority Date Filing Date
US16/750,745 Abandoned US20210180158A1 (en) 2019-01-23 2020-01-23 Ni-Based Superalloy Powder for Additive Manufacturing and an Article Made Therefrom
US17/663,736 Pending US20220349032A1 (en) 2019-01-23 2022-05-17 Ni-Based Superalloy Powder for Additive Manufacturing and an Article Made Therefrom

Family Applications After (1)

Application Number Title Priority Date Filing Date
US17/663,736 Pending US20220349032A1 (en) 2019-01-23 2022-05-17 Ni-Based Superalloy Powder for Additive Manufacturing and an Article Made Therefrom

Country Status (4)

Country Link
US (2) US20210180158A1 (en)
EP (1) EP3914453A1 (en)
KR (1) KR102534546B1 (en)
WO (1) WO2020154494A1 (en)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6054096A (en) * 1982-12-27 2000-04-25 United Technologies Corporation Stable heat treatable nickel superalloy single crystal articles and compositions
US4908183A (en) * 1985-11-01 1990-03-13 United Technologies Corporation High strength single crystal superalloys
US5151249A (en) 1989-12-29 1992-09-29 General Electric Company Nickel-based single crystal superalloy and method of making
EP0789087B1 (en) * 1996-02-09 2000-05-10 Hitachi, Ltd. High strength Ni-base superalloy for directionally solidified castings
JP2003094443A (en) * 2001-07-16 2003-04-03 Tokai Model:Kk Mold and method for manufacturing the same
CN1680611A (en) * 2004-04-07 2005-10-12 联合工艺公司 Oxidation resistant superalloy and article
US8986604B2 (en) 2010-10-20 2015-03-24 Materials Solutions Heat treatments of ALM formed metal mixes to form super alloys
US20160348216A1 (en) 2014-12-16 2016-12-01 Honeywell International Inc. Nickel-based superalloys and additive manufacturing processes using nickel-based superalloys
EP3156164A1 (en) 2015-10-14 2017-04-19 Siemens Aktiengesellschaft Method of producing a workpiece using generative manufacturing ; corresponding workpiece
EP3257956B2 (en) * 2016-06-13 2022-02-16 General Electric Technology GmbH Ni-base superalloy composition and method for slm processing such ni-base superalloy composition

Also Published As

Publication number Publication date
EP3914453A1 (en) 2021-12-01
KR102534546B1 (en) 2023-05-18
KR20210114478A (en) 2021-09-23
WO2020154494A1 (en) 2020-07-30
US20220349032A1 (en) 2022-11-03

Similar Documents

Publication Publication Date Title
US11193187B2 (en) Nickel-based superalloy and parts made from said superalloy
EP2503013B1 (en) Heat-resistant superalloy
EP0577316B1 (en) Single crystal nickel-based superalloy
US20070227630A1 (en) Nickel-based alloy
CN111051548B (en) Precipitation hardenable cobalt-nickel based superalloys and articles made therefrom
JP7138689B2 (en) High-temperature, scratch-resistant superalloys, products made from the alloys, and methods of making the alloys
JPWO2008032751A1 (en) Ni-based single crystal superalloy
EP3208354B1 (en) Ni-based superalloy for hot forging
WO2015159166A1 (en) Gamma - gamma prime strengthened tungsten free cobalt-based superalloy
US20210340644A1 (en) Ni-Based Alloy Softened Powder and Method for Manufacturing Same
EP3208355B1 (en) Ni-based superalloy for hot forging
KR102332018B1 (en) High temperature titanium alloy and method for manufacturing the same
US20220349032A1 (en) Ni-Based Superalloy Powder for Additive Manufacturing and an Article Made Therefrom
US12024758B2 (en) Nickel-based superalloy and parts made from said superalloy
JP7128916B2 (en) Additive manufacturing
US20240110261A1 (en) TiAl ALLOY, TiAl ALLOY POWDER, TiAl ALLOY COMPONENT, AND PRODUCTION METHOD OF THE SAME
RU2771192C1 (en) Powder of a cobalt-based alloy, sintered body made of a cobalt-based alloy, and method for manufacturing a sintered body from a cobalt-based alloy
RU2771192C9 (en) Cobalt-based alloy powder, cobalt-based alloy sintered body, and method for producing cobalt-based alloy sintered body
US20230332278A1 (en) Alloy Material, Alloy Product Formed of Alloy Material, and Mechanical Device Including Alloy Product
EP4159360A1 (en) Cobalt-based alloy product and method for producing cobalt-based alloy product
JP2021134419A (en) Ni-BASED HEAT RESISTANT ALLOY

Legal Events

Date Code Title Description
AS Assignment

Owner name: CRS HOLDINGS, INC., DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ZHOU, NING;STRITCH, KYLE B.;WANG, TAO;AND OTHERS;SIGNING DATES FROM 20200131 TO 20200204;REEL/FRAME:051847/0545

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

AS Assignment

Owner name: CRS HOLDINGS, LLC, DELAWARE

Free format text: ENTITY CONVERSION;ASSIGNOR:CRS HOLDINGS, INC.;REEL/FRAME:059002/0754

Effective date: 20210630

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION