US20180245186A1 - Titanium alloys for additive manufacturing - Google Patents
Titanium alloys for additive manufacturing Download PDFInfo
- Publication number
- US20180245186A1 US20180245186A1 US15/905,531 US201815905531A US2018245186A1 US 20180245186 A1 US20180245186 A1 US 20180245186A1 US 201815905531 A US201815905531 A US 201815905531A US 2018245186 A1 US2018245186 A1 US 2018245186A1
- Authority
- US
- United States
- Prior art keywords
- weight
- titanium alloy
- titanium
- alloy
- less
- 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
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/34—Process control of powder characteristics, e.g. density, oxidation or flowability
-
- B22F3/1055—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/34—Laser welding for purposes other than joining
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/34—Laser welding for purposes other than joining
- B23K26/342—Build-up welding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
- B23K26/354—Working by laser beam, e.g. welding, cutting or boring for surface treatment by melting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
- B23K35/325—Ti as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE 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
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/25—Direct deposition of metal particles, e.g. direct metal deposition [DMD] or laser engineered net shaping [LENS]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/20—Refractory metals
- B22F2301/205—Titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/08—Non-ferrous metals or alloys
- B23K2103/14—Titanium or alloys thereof
-
- B23K2203/14—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE 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
- B33Y10/00—Processes of additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Definitions
- additive manufacturing also known as 3D free form manufacturing, digital manufacturing, direct metal deposition, shaped metal deposition, etc.
- additive manufacturing refers to a process of joining materials to make three-dimensional (3D) objects as opposed to subtractive manufacturing methodologies, such as machining.
- 3D printing represents one form of additive manufacturing.
- Additive manufacturing includes incremental additions of materials in designated locations, often one layer at a time.
- a “build direction” of the object refers to the direction in which the incremental materials are successively added or stacked.
- Known apparatuses for additive manufacturing include powder bed systems, powder feed systems, wire feed systems, etc., such as described in Frazier, William E. “Metal additive manufacturing: A review.” Journal of Materials Engineering and Performance 23, no. 6 (2014): 1917-1928, incorporated herein by reference.
- Additive manufacturing presents benefits over known processes intended to manufacture complex parts from costly materials, such as metal alloys. Additive manufacturing allows significant reduction in scrap produced using subtractive manufacturing. Instead of machining a part from a work piece of solid material, additive manufacturing uses the amount or nearly the amount of material needed to yield a net-shape or near net-shape part.
- AM of traditional titanium alloys produces coarse columnar grains.
- the coarse columnar grains produce undesirable anisotropic mechanical properties in AM components.
- post deposition HIP'ing or heat-treatments are performed which adds another step (and cost) to the manufacturing process and limits placing the as-deposited component directly into service. This is limiting the full exploitation of titanium alloy additive manufactured components.
- the columnar grain structure in AM titanium components can be reduced or eliminated.
- CP Ti commercially pure titanium
- existing titanium alloys with alloying additions
- the columnar grain structure in AM titanium components can be reduced or eliminated.
- an effective amount of a beta eutectoid stabilizer one can form titanium alloys which produce an equiaxed grain structure when melted or sintered during an additive manufacturing process. Using these alloys, the anisotropic mechanical properties of AM components can be reduced or eliminated.
- builds produced using existing titanium alloys are typically post-deposition HIP'ed and/or heat-treated to breakdown their columnar grain structure.
- beta eutectoid stabilizer in the titanium alloy, the columnar grain structure (and by extension the anisotropic mechanical properties) of the build can be reduced or eliminated. Therefore, builds can be put directly into service without the need for extra post-deposition steps, saving time and money.
- titanium alloys for use in additive manufacturing that comprise a titanium material and a beta eutectoid stabilizer.
- the beta eutectoid stabilizer can be present in an effective amount to produce an equiaxed grain structure when the titanium alloy is melted or sintered during an additive manufacturing process.
- the titanium alloy can be in the form of a population of particles having an average particle size suitable for use in conjunction with an additive manufacturing process (e.g., an average particle size of less than about 250 microns).
- the titanium alloy can be in the form of a population of particles having an average particle size of from 5 microns to 200 microns (e.g., from 25 microns to 150 microns, or from 50 microns to 150 microns).
- the beta eutectoid stabilizer can be present in an amount of from 2% to 20% by weight (e.g., greater than 3% to 15% by weight), based on the total weight of the titanium alloy.
- the beta eutectoid stabilizer can be chosen from Fe, Ni, Cu, or a combination thereof.
- the beta eutectoid stabilizer can comprise Fe.
- the Fe can be present in an amount of from 3% to 15% by weight (e.g., from 4% to 6% by weight), based on the total weight of the titanium alloy.
- the beta eutectoid stabilizer can comprise Cu.
- the Cu can be present in an amount of from 3.5% to 10% by weight (e.g., from 4% to 6% by weight), based on the total weight of the titanium alloy.
- the beta eutectoid stabilizer can comprise Ni.
- the Ni can be present in an amount of from 2% to 12% by weight (e.g., from 3% to 6% by weight), based on the total weight of the titanium alloy.
- the titanium material can comprise commercially pure titanium metal or a titanium alloy (e.g., a commercially available titanium alloy). In some embodiments, the titanium material can comprise at least 75% by weight titanium, based on the total weight of the titanium material. In certain embodiments, the titanium material is commercially pure titanium. In other embodiments, the titanium material is a commercially available titanium alloy (e.g., Ti64 (Ti-6Al-4V), Ti18 (Ti-5.5Al-5Mo-5V-2.3Cr-0.8Fe), or a combination thereof).
- Ti64 Ti-6Al-4V
- Ti18 Ti-5.5Al-5Mo-5V-2.3Cr-0.8Fe
- the titanium alloys described herein can produce an equiaxed grain structure when melted or sintered during an additive manufacturing process.
- the titanium alloys described herein can provide objects (builds) that exhibit an average grain aspect ratio of less than 2.5, such as from 1.5 to 2.25.
- the titanium alloys described herein can provide objects (builds) having grains, and at least 85% of the grains have an aspect ratio of less than 3:1.
- FIG. 1A shows the columnar grain structure of a build formed by AM using a conventional commercially available titanium alloy (Ti18; Ti-5.5Al-5Mo-5V-2.3Cr-0.8Fe).
- FIG. 1B is a line drawing showing the outline of grains in a portion of the build shown in FIG. 1A .
- FIG. 2A is an EBSD image quality map showing the grain boundaries in a build formed by AM using Ti18.
- FIG. 2B is an inverse pole figure map showing the orientation of the columnar grains parallel to the build direction in a build formed by AM using Ti18.
- FIG. 2C is a pole figure showing the highly textured columnar grains in a build formed by AM using Ti18.
- FIG. 3A shows the grain structure of a build formed by AM using a titanium alloy comprising Ti18 and varying amounts of iron (ranging from 0.87% by weight Fe to 5.32% by weight Fe).
- FIG. 3B shows the grain structure of a build formed by AM using a titanium alloy comprising Ti18 and varying amounts of iron (ranging from 0.36% by weight Fe to 20.71% by weight Fe).
- FIG. 3C shows a line drawing of the grain boundaries of a portion of the build including 4.44% by weight iron.
- FIG. 4A is an EBSD image quality map showing the grain boundaries in a build formed by AM using Ti18+Fe.
- FIG. 4B is an inverse pole figure map showing the orientation of the grains parallel to the build direction in a build formed by AM using Ti18+Fe.
- FIG. 4C is a pole figure showing the reduction in texture due to the breakdown of the columnar grains (as an equiaxed grain structure is formed) in a build formed by AM using Ti18+Fe.
- FIG. 5 shows the grain structure of a build formed by AM using a titanium alloy comprising Ti18 and varying amounts of copper (ranging from 0.04% by weight Cu to 17.41% by weight Cu).
- FIG. 6A shows the grain structure of a build formed by AM using a titanium alloy comprising Ti18 and varying amounts of nickel (ranging from 0.08% by weight Ni to 3.45% by weight Ni).
- FIG. 6B shows a line drawing of the grain boundaries of a portion of a build including Ti18+2.41% by weight nickel.
- FIGS. 7A-7F show line drawings of the grain boundaries of portions of builds including Ti64+varying amounts of beta eutectoid stabilizer (Fe, Ni, or Cu). In these cases, equiaxed grain structures were observed.
- FIGS. 8A-8C show line drawings of the grain boundaries of portions of builds including CP Ti+varying amounts of beta eutectoid stabilizer (Fe or Fe and Ni). In these cases, equiaxed grain structures were observed.
- the titanium alloys can comprise a titanium material and a beta eutectoid stabilizer.
- the titanium alloy can comprise at least 50% by weight (e.g., at least 55% by weight, at least 60% by weight, at least 65% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, or at least 90% by weight) titanium, based on the total weight of the titanium alloy.
- the titanium alloy can comprise 95% by weight or less (e.g., 90% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less, 60% by weight or less, or 55% by weight or less) titanium, based on the total weight of the titanium alloy.
- the titanium alloy can comprise an amount of titanium ranging from any of the minimum values described above to any of the maximum values described above.
- the titanium alloy can comprise from 50% by weight to 95% by weight titanium (e.g., from 70% by weight to 90% by weight titanium), based on the total weight of the titanium alloy.
- the titanium alloy can be in the form of a population of particles suitable for use in an AM process.
- the titanium alloy can be in the form of a population of particles having an average particle size of less than about 250 microns (e.g., less than 225 microns, less than 200 microns, less than 175 microns, less than 150 microns, less than 125 microns, less than 100 microns, less than 75 microns, less than 50 microns, less than 25 microns, less than 20 microns, or less than 10 microns).
- the titanium alloy can be in the form of a population of particles having an average particle size of at least 5 microns (e.g., at least 10 microns, at least 20 microns, at least 25 microns, at least 50 microns, at least 75 microns, at least 100 microns, at least 125 microns, at least 150 microns, at least 175 microns, at least 200 microns, or at least 225 microns).
- at least 5 microns e.g., at least 10 microns, at least 20 microns, at least 25 microns, at least 50 microns, at least 75 microns, at least 100 microns, at least 125 microns, at least 150 microns, at least 175 microns, at least 200 microns, or at least 225 microns.
- the titanium alloy can be in the form of a population of particles having an average particle size ranging from any of the minimum values described above to any of the maximum values described above.
- the titanium alloy can be in the form of a population of particles having an average particle size of from 5 microns to 200 microns (e.g., from 25 microns to 150 microns, or from 50 microns to 150 microns).
- the average particle size of a population of particles can be measured using, for example, dynamic light scattering.
- Beta eutectoid stabilizers are known in the art, and include Fe, Ni, Cu, Cr, Si, Mn, W, Pd, and Bi.
- the beta eutectoid stabilizer is chosen from Fe, Ni, Cu, or a combination thereof.
- only a single beta eutectoid stabilizer can be incorporated into the titanium alloy.
- a combination of two beta eutectoid stabilizers can be incorporated into the titanium alloy.
- a combination of three beta eutectoid stabilizers can be incorporated into the titanium alloy.
- a combination of four beta eutectoid stabilizers can be incorporated into the titanium alloy.
- the beta eutectoid stabilizers can be present in the titanium alloy in an effective amount to produce an equiaxed grain structure when the titanium alloy is melted or sintered during an additive manufacturing process.
- the beta eutectoid stabilizers can be present in an amount of at least 2% by weight (e.g., at least 2.25% by weight, at least 2.5% by weight, at least 2.75% by weight, at least 3% by weight, at least 3.25% by weight, at least 3.5% by weight, at least 3.75% by weight, at least 4% by weight, at least 4.25% by weight, at least 4.5% by weight, at least 4.75% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight, at least 9% by weight, at least 10% by weight, at least 11% by weight, at least 12% by weight, at least 13% by weight, at least 14% by weight, or at least 15% by weight), based on the total weight of the titanium alloy.
- the beta eutectoid stabilizers can be present in an amount of 20% by weight or less (e.g., 15% by weight or less, 14% by weight or less, 13% by weight or less, 12% by weight or less, 11% by weight or less, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4.75% by weight or less, 4.5% by weight or less, 4.25% by weight or less, 4% by weight or less, 3.75% by weight or less, 3.5% by weight or less, 3.25% by weight or less, 3% by weight or less, 2.75% by weight or less, 2.5% by weight or less, or 2.25% by weight or less), based on the total weight of the titanium alloy.
- 20% by weight or less e.g., 15% by weight or less, 14% by weight or less, 13% by weight or less, 12% by weight or less, 11% by weight or less, 10% by weight or less,
- the beta eutectoid stabilizers can be present in the titanium alloy in an amount ranging from any of the minimum values described above to any of the maximum values described above.
- the beta eutectoid stabilizers can be present in an amount of from 2% to 20% by weight (e.g., greater than 3% to 15% by weight), based on the total weight of the titanium alloy.
- the beta eutectoid stabilizer can comprise iron. In certain embodiments, the beta eutectoid stabilizer can consist of iron. In other embodiments, the beta eutectoid stabilizer can comprise iron in combination with an additional beta eutectoid stabilizer (e.g., Ni or Cu). In other embodiments, the beta eutectoid stabilizer can comprise iron in combination with two additional beta eutectoid stabilizers (e.g., Ni and Cu). In other embodiments, the beta eutectoid stabilizer can comprise iron in combination with three or more additional beta eutectoid stabilizers.
- an additional beta eutectoid stabilizer e.g., Ni or Cu
- the beta eutectoid stabilizer can comprise iron in combination with two additional beta eutectoid stabilizers (e.g., Ni and Cu). In other embodiments, the beta eutectoid stabilizer can comprise iron in combination with three or more additional
- Fe can be present in an amount of at least 3% by weight (e.g., at least 3.25% by weight, at least 3.5% by weight, at least 3.75% by weight, at least 4% by weight, at least 4.25% by weight, at least 4.5% by weight, at least 4.75% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight, at least 9% by weight, at least 10% by weight, at least 11% by weight, at least 12% by weight, at least 13% by weight, at least 14% by weight, or at least 15% by weight), based on the total weight of the titanium alloy.
- at least 3% by weight e.g., at least 3.25% by weight, at least 3.5% by weight, at least 3.75% by weight, at least 4% by weight, at least 4.25% by weight, at least 4.5% by weight, at least 4.75% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight
- Fe can be present in an amount of 15% by weight or less (e.g., 14% by weight or less, 13% by weight or less, 12% by weight or less, 11% by weight or less, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4.75% by weight or less, 4.5% by weight or less, 4.25% by weight or less, 4% by weight or less, 3.75% by weight or less, 3.5% by weight or less, or 3.25% by weight or less), based on the total weight of the titanium alloy.
- 15% by weight or less e.g., 14% by weight or less, 13% by weight or less, 12% by weight or less, 11% by weight or less, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4.75% by weight or less, 4.5% by weight or less, 4.25% by
- Iron can be present in the titanium alloy in an amount ranging from any of the minimum values described above to any of the maximum values described above.
- Fe can be present in an amount of from 3% to 15% by weight (e.g., from 4% to 6% by weight), based on the total weight of the titanium alloy.
- the beta eutectoid stabilizer can comprise copper. In certain embodiments, the beta eutectoid stabilizer can consist of copper. In other embodiments, the beta eutectoid stabilizer can comprise copper in combination with an additional beta eutectoid stabilizer (e.g., Ni or Fe). In other embodiments, the beta eutectoid stabilizer can comprise copper in combination with two additional beta eutectoid stabilizers (e.g., Ni and Fe). In other embodiments, the beta eutectoid stabilizer can comprise copper in combination with three or more additional beta eutectoid stabilizers.
- additional beta eutectoid stabilizer e.g., Ni or Fe
- the beta eutectoid stabilizer can comprise copper in combination with two additional beta eutectoid stabilizers (e.g., Ni and Fe).
- Cu can be present in an amount of at least 3.5% by weight (e.g., at least 3.75% by weight, at least 4% by weight, at least 4.25% by weight, at least 4.5% by weight, at least 4.75% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight, at least 9% by weight, at least 10% by weight, at least 11% by weight, at least 12% by weight, at least 13% by weight, at least 14% by weight, or at least 15% by weight), based on the total weight of the titanium alloy.
- at least 3.5% by weight e.g., at least 3.75% by weight, at least 4% by weight, at least 4.25% by weight, at least 4.5% by weight, at least 4.75% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight, at least 9% by weight, at least 10% by weight, at least 11% by weight, at least 12% by weight, at least
- Cu can be present in an amount of 10% by weight or less (e.g., 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4.75% by weight or less, 4.5% by weight or less, 4.25% by weight or less, 4% by weight or less, or 3.75% by weight or less), based on the total weight of the titanium alloy.
- 10% by weight or less e.g., 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4.75% by weight or less, 4.5% by weight or less, 4.25% by weight or less, 4% by weight or less, or 3.75% by weight or less
- Copper can be present in the titanium alloy in an amount ranging from any of the minimum values described above to any of the maximum values described above.
- Cu can be present in an amount of from 3.5% to 10% by weight (e.g., from 4% to 6% by weight), based on the total weight of the titanium alloy.
- the beta eutectoid stabilizer can comprise nickel. In certain embodiments, the beta eutectoid stabilizer can consist of nickel. In other embodiments, the beta eutectoid stabilizer can comprise nickel in combination with an additional beta eutectoid stabilizer (e.g., Fe or Cu). In other embodiments, the beta eutectoid stabilizer can comprise nickel in combination with two additional beta eutectoid stabilizers (e.g., Fe and Cu). In other embodiments, the beta eutectoid stabilizer can comprise nickel in combination with three or more additional beta eutectoid stabilizers.
- additional beta eutectoid stabilizer e.g., Fe or Cu
- the beta eutectoid stabilizer can comprise nickel in combination with two additional beta eutectoid stabilizers (e.g., Fe and Cu).
- Ni can be present in an amount of at least 2% by weight (e.g., at least 2.25% by weight, at least 2.5% by weight, at least 2.75% by weight, at least 3% by weight, at least 3.25% by weight, at least 3.5% by weight, at least 3.75% by weight, at least 4% by weight, at least 4.25% by weight, at least 4.5% by weight, at least 4.75% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight, at least 9% by weight, at least 10% by weight, or at least 11% by weight), based on the total weight of the titanium alloy.
- at least 2% by weight e.g., at least 2.25% by weight, at least 2.5% by weight, at least 2.75% by weight, at least 3% by weight, at least 3.25% by weight, at least 3.5% by weight, at least 3.75% by weight, at least 4% by weight, at least 4.25% by weight, at least 4.5% by weight, at least
- Ni can be present in an amount of 12% by weight or less (e.g., 11% by weight or less, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4.75% by weight or less, 4.5% by weight or less, 4.25% by weight or less, 4% by weight or less, 3.75% by weight or less, 3.5% by weight or less, 3.25% by weight or less, 3% by weight or less, 2.75% by weight or less, 2.5% by weight or less, or 2.25% by weight or less), based on the total weight of the titanium alloy.
- 12% by weight or less e.g., 11% by weight or less, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4.75% by weight or less, 4.5% by weight or less, 4.25% by weight or less, 4% by weight or less
- Nickel can be present in the titanium alloy in an amount ranging from any of the minimum values described above to any of the maximum values described above.
- Ni can be present in an amount of from 2% to 12% by weight (e.g., from 3% to 6% by weight), based on the total weight of the titanium alloy.
- the titanium material can comprise any suitable titanium or titanium alloy.
- the titanium material can comprise commercially pure titanium.
- commercially pure titanium refers to a titanium material in which the amount of titanium is at least about 98% by weight (e.g., at least 98.5% by weight, at least 99% by weight, or at least 99.5% by weight) of the material.
- the titanium material can comprise a titanium alloy.
- the titanium material can comprise at least 50% by weight (e.g., at least 55% by weight, at least 60% by weight, at least 65% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, or at least 95% by weight) titanium, based on the total weight of the titanium material.
- the titanium material can comprise 95% by weight or less (e.g., 90% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less, 60% by weight or less, or 55% by weight or less) titanium, based on the total weight of the titanium material.
- 95% by weight or less e.g., 90% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less, 60% by weight or less, or 55% by weight or less
- the titanium material can comprise an amount of titanium ranging from any of the minimum values described above to any of the maximum values described above.
- the titanium material can comprise from 50% by weight to 95% by weight titanium (e.g., from 70% by weight to 90% by weight titanium), based on the total weight of the titanium material.
- the titanium material can comprise a commercially available titanium alloy. Examples of commercially available titanium alloys are shown in Table 1 below.
- the titanium material can comprise Ti64 (Ti-6Al-4V), Ti18 (Ti-5.5Al-5Mo-5V-2.3Cr-0.8Fe), or a combination thereof.
- Alloy Alloy Composition Ti64 Ti—6Al—4V Ti18 Ti—5.5Al—5Mo—5V—2.3Cr—0.8Fe Ti6246 Ti—6Al—2Sn—4Zr—6Mo Ti6242 Ti—6Al—2Sn—4Zr—2Mo Ti17 Ti—5Al—2Sn—4Mo—2Zr—4Cr ⁇ 21S Ti—15Mo—3Nb—3Al—0.2Si Ti-10-2-3 Ti—10V—2Fe—3Al Ti-5111 Ti—5Al—1Sn—1V—1Zr—1Mo Ti-3-2.5 Ti—3Al—2.5V Ti62S Ti—6Al—1.65Fe Ti550 Ti—4Al—4Mo—2Sn—.5Si NiTi Ti—55Ni NiTiFe Ti—53Ni—3.5Fe
- AM processes include a variety of processes which result in useful, three-dimensional objects and include a step of sequentially forming the shape of the object one layer at a time.
- AM processes include, for example, processes employing powders as a feedstock such as selective laser melting (SLM), selective laser sintering (SLS), electron beam melting (EBM), and electron beam sintering (EBS).
- SLM selective laser melting
- SLS selective laser sintering
- EBM electron beam melting
- EBS electron beam sintering
- Other examples of such AM processes include Powder Directed Energy Deposition methods, such as Laser Engineering Net Shape (LENS) and Laser Metal Deposition-powder (LIVID-p) methods.
- These processes generally provide for the rapid manufacture a three-dimensional object (e.g., an article, component, part, product, etc.) through the sequential formation of a multiplicity of thin unit layers. More specifically, layers of a powder material are laid down and irradiated with an energy beam (e.g., laser beam) so that particles of the powder material within each layer are sequentially sintered (fused) or melted to solidify the layer.
- an energy beam e.g., laser beam
- laser sintering/melting technology can be found, for example, in U.S. Pat. No. 4,863,538, U.S. Pat. No. 5,017,753, U.S. Pat. No. 5,076,869, and U.S. Pat. No. 4,944,817, each of which are hereby incorporated herein by reference in its entirety.
- a laser beam is used to selectively fuse a powder material by scanning cross-sections of the material in a bed. These cross-sections are scanned based on a three-dimensional description of the desired object. This description may be obtained from various sources such as, for example, a computer aided design (CAD) file, scan data, or some other source.
- CAD computer aided design
- Electron sintering/melting technology operates using similar principles, except that an electron beam is used in place of a laser beam to locally transfer energy to the powder material.
- additive manufacturing processes that can utilize the titanium alloys described herein include wire-based AM processes (i.e., wire directed energy deposition methods, such as Laser Metal Deposition-wire (LMD-w) and Electron Beam Additive Manufacturing (EBAM®) methods).
- wire directed energy deposition methods such as Laser Metal Deposition-wire (LMD-w) and Electron Beam Additive Manufacturing (EBAM®) methods.
- LMD-w Laser Metal Deposition-wire
- EBAM® Electron Beam Additive Manufacturing
- Methods of forming objects via additive manufacturing processes can comprise applying energy to a first quantity of a powdered titanium alloy described herein on a substrate so as to fuse particles of the powdered titanium alloy into a first layer on the substrate; and forming at least one additional layer on the first layer by applying energy to at least a second quantity of a powdered titanium alloy described herein on the first layer so as to fuse particles of the powdered titanium alloy into the at least one additional layer on the first layer, thereby forming the object.
- Applying energy can comprise contacting the powdered titanium alloy with a laser beam or an electron beam (depending upon the additive manufacturing process employed).
- Methods of forming objects via additive manufacturing processes can also comprise directing an energy beam and feeding a feedstock comprising a titanium alloy described herein to a feed point adjacent to a substrate, thereby forming a molten puddle; moving the feed point relative to the substrate, thereby advancing the molten puddle of presently fed feedstock and rapidly solidifying previously fed feedstock; and sequentially advancing the feed point within a predetermined geometric volume, thereby sequentially fusing the feedstock, by action of the advancing molten puddle, into a near net shape work piece built-up upon the substrate.
- the feedstock can comprise, for example, a wire formed from a titanium alloy described herein.
- equiaxed grain structure refers to a grain structure that includes a population of grains having an average aspect ratio of 3:1 or less. Standard methods for determining the average grain size of grains present in a metal are known in the art. See, for example, ASTM E112-12, entitled “Standard Test Methods for Determining Average Grain Size,” which is hereby incorporated herein by reference in its entirety. The average aspect ratio of grains can be calculated from the grain dimensions obtained using ASTM E112-12.
- the object can exhibit an average grain aspect ratio of less than 2.5:1 (e.g., less than 2.25:1, less than 2:1, less than 1.9:1, less than 1.8:1, less than 1.7:1, less than 1.6:1, less than 1.5:1, less than 1.4:1, less than 1.3:1, or less). In some embodiments, the object can exhibit an average grain aspect ratio of greater than 1:1 (e.g., at least 1.3:1, at least 1.4:1, at least 1.5:1, at least 1.6:1, at least 1.7:1, at least 1.8:1, at least 1.9:1, at least 2:1, or at least 2.25:1). In some embodiments, the object can exhibit an average grain aspect ratio of about 1:1.
- the object can exhibit an average grain aspect ratio ranging from any of the minimum values described above to any of the maximum values described above.
- the object can exhibit an average grain aspect ratio of from 1.5 to 2.25.
- the standard deviation of the average grain aspect ratio can be less than 1.
- the object comprises grains, and at least 85% (e.g., at least 90%, or at least 95%) of the grains have an aspect ratio of less than 3:1. In some embodiments, the object comprises grains, and at least 85% (e.g., at least 90%, or at least 95%) of the grains have an aspect ratio of less than 2.5:1. In some embodiments, the object comprises grains, and at least 85% (e.g., at least 90%, or at least 95%) of the grains have an aspect ratio of less than 2:1.
- the beta eutectoid stabilizer can be added in an effective amount to produce an equiaxed grain structure when the titanium alloy is melted or sintered during an additive manufacturing process.
- the method can further comprise micronizing the titanium alloy to form a population of particles suitable for use in an additive manufacturing process.
- An Optomec Laser Engineered Net Shaping (LENSTM) additive manufacturing device with two powder feeders was used to deposit single composition and compositionally graded cylinders using pre-alloyed and elemental powders.
- the pre-alloyed powders included commercially pure titanium (CP Ti), Ti-6Al-4V and Ti18 and the elemental powders were iron, nickel and copper.
- Custom elemental blend powders made by mixing the pre-alloyed and elemental powders in the correct ratio for the desired composition, were also used.
- powder feeder one contained the pre-alloyed powder and powder feeder two contained the elemental blend.
- the rpm (flow rate control reference for The Ohio State University LENSTM) of powder feeder one was set to three and the rpm of powder feeder two was set to zero.
- the rpm of powder feeder one was decreased while the rpm of powder feeder two was increased by the same amount.
- the rpm change was done in a stepwise function to create distinct composition layers.
- the laser power varied between 300 W and 325 W depending on the composition.
- the travel speed was set at 20′′/min, the layer spacing was 0.010′′ and the hatch width was 0.015′′.
- the specimens were sectioned parallel to the build direction and the plane parallel to the build direction was polished through 0.05 um colloidal silica.
- the as-deposited specimens were characterized using an FEI Apreo scanning electron microscope (SEM).
- BSE Backscattered electron
- XEDS X-ray energy dispersive spectroscopy
- EBSD Hikari electron backscattered diffraction
- OIM Data Collection 7.0 was used for acquiring grain orientation data.
- the orientation data was analyzed using OIM Data Analysis 8.0.
- the individual grains were manually separated along the grain boundary alpha. If there was no grain boundary alpha present, a grain boundary map from the EBSD orientation data was used. Using the image analysis program MIPAR and its Feature Measurements tool, the major axis length and minor axis length of each grain was determined. The aspect ratio was calculated by dividing the major axis length by the minor axis length. All edge grains were removed from the image before quantification. The texture of the beta grains was calculated if more than half of the data points were the beta phase.
- FIG. 2A is an image quality (IQ) map of as-deposited Ti18.
- the IQ map is based on the pattern quality of the EBSD data. Lower pattern quality results in a lower IQ value and is therefore a darker point in the IQ map. Grain boundaries typically have low quality and therefore can be used for grain identification.
- the darker lines in FIG. 2A are the grain boundaries of the columnar grains.
- FIG. 2B is an inverse pole figure (IPF) map of the selected area.
- An IPF map shows the grain orientation relative to the sample normal, rolling or transverse direction.
- the pole figure FIG. 2C ) shows the preferred orientation of the columnar grains with a times random value of 28.6. The times random value is the ratio of the actual measured grain orientation and a calculated truly random grain orientation. The higher the times random value, the greater the amount of texture in the build.
- FIGS. 3A and 3B Builds was performed using Ti18 containing varying amounts of Fe.
- the resulting grain structures are shown in FIGS. 3A and 3B .
- columnar grains were formed.
- the addition of increasing amounts of Fe to Ti18 produced an equiaxed grain structure along the build direction.
- FIG. 4A is an image quality map showing the grain boundaries.
- FIG. 4B is an inverse pole figure (IPF) map of the selected area.
- FIG. 4C shows the pole figure (PF) of the scanned area with a times random value of 7.426, which is less than the Ti18 as-deposited times random value of 28.6. This indicates that the columnar structure has broken down upon the addition of iron, and an equiaxed structure has now formed.
- FIG. 6A shows a line drawing of the grain boundaries of a portion of a build including Ti18+2.41% by weight nickel. The structure appeared equiaxed. The grain structure of the region of the build was analyzed statistically. The results are included in the table below.
- FIGS. 7A-7F show line drawings of the grain boundaries of portions of these builds. The grain structure of regions of these builds were analyzed statistically and were found to be equiaxed. The results are included in the table below.
- FIGS. 8A-8C show line drawings of the grain boundaries of portions of these builds. The grain structure of regions of these builds were analyzed statistically and were found to be equiaxed. The results are included in the table below.
- compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims. Any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative compositions and method steps disclosed herein are specifically described, other combinations of the compositions and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein or less, however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
- This application claims benefit of U.S. Provisional Application No. 62/463,338, filed Feb. 24, 2017, which is hereby incorporated herein by reference in its entirety.
- “Additive manufacturing” (AM), also known as 3D free form manufacturing, digital manufacturing, direct metal deposition, shaped metal deposition, etc., refers to a process of joining materials to make three-dimensional (3D) objects as opposed to subtractive manufacturing methodologies, such as machining. 3D printing represents one form of additive manufacturing. Additive manufacturing includes incremental additions of materials in designated locations, often one layer at a time. A “build direction” of the object refers to the direction in which the incremental materials are successively added or stacked. Known apparatuses for additive manufacturing include powder bed systems, powder feed systems, wire feed systems, etc., such as described in Frazier, William E. “Metal additive manufacturing: A review.” Journal of Materials Engineering and Performance 23, no. 6 (2014): 1917-1928, incorporated herein by reference.
- Additive manufacturing presents benefits over known processes intended to manufacture complex parts from costly materials, such as metal alloys. Additive manufacturing allows significant reduction in scrap produced using subtractive manufacturing. Instead of machining a part from a work piece of solid material, additive manufacturing uses the amount or nearly the amount of material needed to yield a net-shape or near net-shape part.
- Even so, objects produced from additive manufacturing exhibit unique metallurgical and mechanical properties. Although dimensions of an additive manufactured part may be accurately and precisely produced within tolerances, the part may lack the mechanical properties desired given the incremental additions of material. As a result, further additive manufacturing techniques are desired that enhance metallurgical and/or mechanical properties.
- As shown in
FIG. 1A , AM of traditional titanium alloys produces coarse columnar grains. The coarse columnar grains produce undesirable anisotropic mechanical properties in AM components. To break down the columnar structure, post deposition HIP'ing or heat-treatments are performed which adds another step (and cost) to the manufacturing process and limits placing the as-deposited component directly into service. This is limiting the full exploitation of titanium alloy additive manufactured components. - By modifying pure commercially pure titanium (CP Ti) or existing titanium alloys with alloying additions, the columnar grain structure in AM titanium components can be reduced or eliminated. Specifically, by incorporating an effective amount of a beta eutectoid stabilizer, one can form titanium alloys which produce an equiaxed grain structure when melted or sintered during an additive manufacturing process. Using these alloys, the anisotropic mechanical properties of AM components can be reduced or eliminated.
- As discussed above, builds produced using existing titanium alloys are typically post-deposition HIP'ed and/or heat-treated to breakdown their columnar grain structure. However, by incorporating beta eutectoid stabilizer in the titanium alloy, the columnar grain structure (and by extension the anisotropic mechanical properties) of the build can be reduced or eliminated. Therefore, builds can be put directly into service without the need for extra post-deposition steps, saving time and money.
- Accordingly, provided herein are titanium alloys for use in additive manufacturing that comprise a titanium material and a beta eutectoid stabilizer. The beta eutectoid stabilizer can be present in an effective amount to produce an equiaxed grain structure when the titanium alloy is melted or sintered during an additive manufacturing process.
- The titanium alloy can be in the form of a population of particles having an average particle size suitable for use in conjunction with an additive manufacturing process (e.g., an average particle size of less than about 250 microns). For example, in some embodiments, the titanium alloy can be in the form of a population of particles having an average particle size of from 5 microns to 200 microns (e.g., from 25 microns to 150 microns, or from 50 microns to 150 microns). The beta eutectoid stabilizer can be present in an amount of from 2% to 20% by weight (e.g., greater than 3% to 15% by weight), based on the total weight of the titanium alloy.
- In some embodiments, the beta eutectoid stabilizer can be chosen from Fe, Ni, Cu, or a combination thereof. In some embodiments, the beta eutectoid stabilizer can comprise Fe. In some of these embodiments, the Fe can be present in an amount of from 3% to 15% by weight (e.g., from 4% to 6% by weight), based on the total weight of the titanium alloy. In some embodiments, the beta eutectoid stabilizer can comprise Cu. In some of these embodiments, the Cu can be present in an amount of from 3.5% to 10% by weight (e.g., from 4% to 6% by weight), based on the total weight of the titanium alloy. In some embodiments, the beta eutectoid stabilizer can comprise Ni. In some of these embodiments, the Ni can be present in an amount of from 2% to 12% by weight (e.g., from 3% to 6% by weight), based on the total weight of the titanium alloy.
- The titanium material can comprise commercially pure titanium metal or a titanium alloy (e.g., a commercially available titanium alloy). In some embodiments, the titanium material can comprise at least 75% by weight titanium, based on the total weight of the titanium material. In certain embodiments, the titanium material is commercially pure titanium. In other embodiments, the titanium material is a commercially available titanium alloy (e.g., Ti64 (Ti-6Al-4V), Ti18 (Ti-5.5Al-5Mo-5V-2.3Cr-0.8Fe), or a combination thereof).
- As discussed above, the titanium alloys described herein can produce an equiaxed grain structure when melted or sintered during an additive manufacturing process. In some embodiments, the titanium alloys described herein can provide objects (builds) that exhibit an average grain aspect ratio of less than 2.5, such as from 1.5 to 2.25. In some embodiments, the titanium alloys described herein can provide objects (builds) having grains, and at least 85% of the grains have an aspect ratio of less than 3:1.
- Also provided are methods of forming objects via additive manufacturing processes as well as methods of forming titanium alloys for use in additive manufacturing.
-
FIG. 1A shows the columnar grain structure of a build formed by AM using a conventional commercially available titanium alloy (Ti18; Ti-5.5Al-5Mo-5V-2.3Cr-0.8Fe). -
FIG. 1B is a line drawing showing the outline of grains in a portion of the build shown inFIG. 1A . -
FIG. 2A is an EBSD image quality map showing the grain boundaries in a build formed by AM using Ti18. -
FIG. 2B is an inverse pole figure map showing the orientation of the columnar grains parallel to the build direction in a build formed by AM using Ti18. -
FIG. 2C is a pole figure showing the highly textured columnar grains in a build formed by AM using Ti18. -
FIG. 3A shows the grain structure of a build formed by AM using a titanium alloy comprising Ti18 and varying amounts of iron (ranging from 0.87% by weight Fe to 5.32% by weight Fe). -
FIG. 3B shows the grain structure of a build formed by AM using a titanium alloy comprising Ti18 and varying amounts of iron (ranging from 0.36% by weight Fe to 20.71% by weight Fe). -
FIG. 3C shows a line drawing of the grain boundaries of a portion of the build including 4.44% by weight iron. -
FIG. 4A is an EBSD image quality map showing the grain boundaries in a build formed by AM using Ti18+Fe. -
FIG. 4B is an inverse pole figure map showing the orientation of the grains parallel to the build direction in a build formed by AM using Ti18+Fe. -
FIG. 4C is a pole figure showing the reduction in texture due to the breakdown of the columnar grains (as an equiaxed grain structure is formed) in a build formed by AM using Ti18+Fe. -
FIG. 5 shows the grain structure of a build formed by AM using a titanium alloy comprising Ti18 and varying amounts of copper (ranging from 0.04% by weight Cu to 17.41% by weight Cu). -
FIG. 6A shows the grain structure of a build formed by AM using a titanium alloy comprising Ti18 and varying amounts of nickel (ranging from 0.08% by weight Ni to 3.45% by weight Ni). -
FIG. 6B shows a line drawing of the grain boundaries of a portion of a build including Ti18+2.41% by weight nickel. -
FIGS. 7A-7F show line drawings of the grain boundaries of portions of builds including Ti64+varying amounts of beta eutectoid stabilizer (Fe, Ni, or Cu). In these cases, equiaxed grain structures were observed. -
FIGS. 8A-8C show line drawings of the grain boundaries of portions of builds including CP Ti+varying amounts of beta eutectoid stabilizer (Fe or Fe and Ni). In these cases, equiaxed grain structures were observed. - Disclosed herein are titanium alloys for use in additive manufacturing. The titanium alloys can comprise a titanium material and a beta eutectoid stabilizer.
- In some embodiments, the titanium alloy can comprise at least 50% by weight (e.g., at least 55% by weight, at least 60% by weight, at least 65% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, or at least 90% by weight) titanium, based on the total weight of the titanium alloy. In some embodiments, the titanium alloy can comprise 95% by weight or less (e.g., 90% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less, 60% by weight or less, or 55% by weight or less) titanium, based on the total weight of the titanium alloy.
- The titanium alloy can comprise an amount of titanium ranging from any of the minimum values described above to any of the maximum values described above. For example, in some embodiments, the titanium alloy can comprise from 50% by weight to 95% by weight titanium (e.g., from 70% by weight to 90% by weight titanium), based on the total weight of the titanium alloy.
- The titanium alloy can be in the form of a population of particles suitable for use in an AM process. For example, the titanium alloy can be in the form of a population of particles having an average particle size of less than about 250 microns (e.g., less than 225 microns, less than 200 microns, less than 175 microns, less than 150 microns, less than 125 microns, less than 100 microns, less than 75 microns, less than 50 microns, less than 25 microns, less than 20 microns, or less than 10 microns). The titanium alloy can be in the form of a population of particles having an average particle size of at least 5 microns (e.g., at least 10 microns, at least 20 microns, at least 25 microns, at least 50 microns, at least 75 microns, at least 100 microns, at least 125 microns, at least 150 microns, at least 175 microns, at least 200 microns, or at least 225 microns).
- The titanium alloy can be in the form of a population of particles having an average particle size ranging from any of the minimum values described above to any of the maximum values described above. For example, in some embodiments, the titanium alloy can be in the form of a population of particles having an average particle size of from 5 microns to 200 microns (e.g., from 25 microns to 150 microns, or from 50 microns to 150 microns). The average particle size of a population of particles can be measured using, for example, dynamic light scattering.
- Beta eutectoid stabilizers are known in the art, and include Fe, Ni, Cu, Cr, Si, Mn, W, Pd, and Bi. In some embodiments, the beta eutectoid stabilizer is chosen from Fe, Ni, Cu, or a combination thereof. In some embodiments, only a single beta eutectoid stabilizer can be incorporated into the titanium alloy. In other embodiments, a combination of two beta eutectoid stabilizers can be incorporated into the titanium alloy. In other embodiments, a combination of three beta eutectoid stabilizers can be incorporated into the titanium alloy. In other embodiments, a combination of four beta eutectoid stabilizers can be incorporated into the titanium alloy.
- The beta eutectoid stabilizers can be present in the titanium alloy in an effective amount to produce an equiaxed grain structure when the titanium alloy is melted or sintered during an additive manufacturing process. In some embodiments, the beta eutectoid stabilizers can be present in an amount of at least 2% by weight (e.g., at least 2.25% by weight, at least 2.5% by weight, at least 2.75% by weight, at least 3% by weight, at least 3.25% by weight, at least 3.5% by weight, at least 3.75% by weight, at least 4% by weight, at least 4.25% by weight, at least 4.5% by weight, at least 4.75% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight, at least 9% by weight, at least 10% by weight, at least 11% by weight, at least 12% by weight, at least 13% by weight, at least 14% by weight, or at least 15% by weight), based on the total weight of the titanium alloy. In some embodiments, the beta eutectoid stabilizers can be present in an amount of 20% by weight or less (e.g., 15% by weight or less, 14% by weight or less, 13% by weight or less, 12% by weight or less, 11% by weight or less, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4.75% by weight or less, 4.5% by weight or less, 4.25% by weight or less, 4% by weight or less, 3.75% by weight or less, 3.5% by weight or less, 3.25% by weight or less, 3% by weight or less, 2.75% by weight or less, 2.5% by weight or less, or 2.25% by weight or less), based on the total weight of the titanium alloy.
- The beta eutectoid stabilizers can be present in the titanium alloy in an amount ranging from any of the minimum values described above to any of the maximum values described above. For example, in some embodiments, the beta eutectoid stabilizers can be present in an amount of from 2% to 20% by weight (e.g., greater than 3% to 15% by weight), based on the total weight of the titanium alloy.
- In some embodiments, the beta eutectoid stabilizer can comprise iron. In certain embodiments, the beta eutectoid stabilizer can consist of iron. In other embodiments, the beta eutectoid stabilizer can comprise iron in combination with an additional beta eutectoid stabilizer (e.g., Ni or Cu). In other embodiments, the beta eutectoid stabilizer can comprise iron in combination with two additional beta eutectoid stabilizers (e.g., Ni and Cu). In other embodiments, the beta eutectoid stabilizer can comprise iron in combination with three or more additional beta eutectoid stabilizers.
- In some embodiments, Fe can be present in an amount of at least 3% by weight (e.g., at least 3.25% by weight, at least 3.5% by weight, at least 3.75% by weight, at least 4% by weight, at least 4.25% by weight, at least 4.5% by weight, at least 4.75% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight, at least 9% by weight, at least 10% by weight, at least 11% by weight, at least 12% by weight, at least 13% by weight, at least 14% by weight, or at least 15% by weight), based on the total weight of the titanium alloy. In some embodiments, Fe can be present in an amount of 15% by weight or less (e.g., 14% by weight or less, 13% by weight or less, 12% by weight or less, 11% by weight or less, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4.75% by weight or less, 4.5% by weight or less, 4.25% by weight or less, 4% by weight or less, 3.75% by weight or less, 3.5% by weight or less, or 3.25% by weight or less), based on the total weight of the titanium alloy.
- Iron can be present in the titanium alloy in an amount ranging from any of the minimum values described above to any of the maximum values described above. For example, in some embodiments, Fe can be present in an amount of from 3% to 15% by weight (e.g., from 4% to 6% by weight), based on the total weight of the titanium alloy.
- In some embodiments, the beta eutectoid stabilizer can comprise copper. In certain embodiments, the beta eutectoid stabilizer can consist of copper. In other embodiments, the beta eutectoid stabilizer can comprise copper in combination with an additional beta eutectoid stabilizer (e.g., Ni or Fe). In other embodiments, the beta eutectoid stabilizer can comprise copper in combination with two additional beta eutectoid stabilizers (e.g., Ni and Fe). In other embodiments, the beta eutectoid stabilizer can comprise copper in combination with three or more additional beta eutectoid stabilizers.
- In some embodiments, Cu can be present in an amount of at least 3.5% by weight (e.g., at least 3.75% by weight, at least 4% by weight, at least 4.25% by weight, at least 4.5% by weight, at least 4.75% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight, at least 9% by weight, at least 10% by weight, at least 11% by weight, at least 12% by weight, at least 13% by weight, at least 14% by weight, or at least 15% by weight), based on the total weight of the titanium alloy. In some embodiments, Cu can be present in an amount of 10% by weight or less (e.g., 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4.75% by weight or less, 4.5% by weight or less, 4.25% by weight or less, 4% by weight or less, or 3.75% by weight or less), based on the total weight of the titanium alloy.
- Copper can be present in the titanium alloy in an amount ranging from any of the minimum values described above to any of the maximum values described above. For example, in some embodiments, Cu can be present in an amount of from 3.5% to 10% by weight (e.g., from 4% to 6% by weight), based on the total weight of the titanium alloy.
- In some embodiments, the beta eutectoid stabilizer can comprise nickel. In certain embodiments, the beta eutectoid stabilizer can consist of nickel. In other embodiments, the beta eutectoid stabilizer can comprise nickel in combination with an additional beta eutectoid stabilizer (e.g., Fe or Cu). In other embodiments, the beta eutectoid stabilizer can comprise nickel in combination with two additional beta eutectoid stabilizers (e.g., Fe and Cu). In other embodiments, the beta eutectoid stabilizer can comprise nickel in combination with three or more additional beta eutectoid stabilizers.
- In some embodiments, Ni can be present in an amount of at least 2% by weight (e.g., at least 2.25% by weight, at least 2.5% by weight, at least 2.75% by weight, at least 3% by weight, at least 3.25% by weight, at least 3.5% by weight, at least 3.75% by weight, at least 4% by weight, at least 4.25% by weight, at least 4.5% by weight, at least 4.75% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight, at least 9% by weight, at least 10% by weight, or at least 11% by weight), based on the total weight of the titanium alloy. In some embodiments, Ni can be present in an amount of 12% by weight or less (e.g., 11% by weight or less, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4.75% by weight or less, 4.5% by weight or less, 4.25% by weight or less, 4% by weight or less, 3.75% by weight or less, 3.5% by weight or less, 3.25% by weight or less, 3% by weight or less, 2.75% by weight or less, 2.5% by weight or less, or 2.25% by weight or less), based on the total weight of the titanium alloy.
- Nickel can be present in the titanium alloy in an amount ranging from any of the minimum values described above to any of the maximum values described above. For example, in some embodiments, Ni can be present in an amount of from 2% to 12% by weight (e.g., from 3% to 6% by weight), based on the total weight of the titanium alloy.
- The titanium material can comprise any suitable titanium or titanium alloy. In some cases, the titanium material can comprise commercially pure titanium. As used herein, the term “commercially pure titanium” refers to a titanium material in which the amount of titanium is at least about 98% by weight (e.g., at least 98.5% by weight, at least 99% by weight, or at least 99.5% by weight) of the material.
- In some embodiments, the titanium material can comprise a titanium alloy. In some embodiments, the titanium material can comprise at least 50% by weight (e.g., at least 55% by weight, at least 60% by weight, at least 65% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, or at least 95% by weight) titanium, based on the total weight of the titanium material. In some embodiments, the titanium material can comprise 95% by weight or less (e.g., 90% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less, 60% by weight or less, or 55% by weight or less) titanium, based on the total weight of the titanium material.
- The titanium material can comprise an amount of titanium ranging from any of the minimum values described above to any of the maximum values described above. For example, in some embodiments, the titanium material can comprise from 50% by weight to 95% by weight titanium (e.g., from 70% by weight to 90% by weight titanium), based on the total weight of the titanium material.
- In certain embodiments, the titanium material can comprise a commercially available titanium alloy. Examples of commercially available titanium alloys are shown in Table 1 below. In certain embodiments, the titanium material can comprise Ti64 (Ti-6Al-4V), Ti18 (Ti-5.5Al-5Mo-5V-2.3Cr-0.8Fe), or a combination thereof.
-
TABLE 1 Composition of commercially available titanium alloys. Alloy Alloy Composition (wt. %) Ti64 Ti—6Al—4V Ti18 Ti—5.5Al—5Mo—5V—2.3Cr—0.8Fe Ti6246 Ti—6Al—2Sn—4Zr—6Mo Ti6242 Ti—6Al—2Sn—4Zr—2Mo Ti17 Ti—5Al—2Sn—4Mo—2Zr—4Cr β21S Ti—15Mo—3Nb—3Al—0.2Si Ti-10-2-3 Ti—10V—2Fe—3Al Ti-5111 Ti—5Al—1Sn—1V—1Zr—1Mo Ti-3-2.5 Ti—3Al—2.5V Ti62S Ti—6Al—1.65Fe Ti550 Ti—4Al—4Mo—2Sn—.5Si NiTi Ti—55Ni NiTiFe Ti—53Ni—3.5Fe - The titanium alloys described herein can be used in a variety of AM processes that employ metallic powders as a feedstock. AM processes include a variety of processes which result in useful, three-dimensional objects and include a step of sequentially forming the shape of the object one layer at a time. Examples of such AM processes include, for example, processes employing powders as a feedstock such as selective laser melting (SLM), selective laser sintering (SLS), electron beam melting (EBM), and electron beam sintering (EBS). Other examples of such AM processes include Powder Directed Energy Deposition methods, such as Laser Engineering Net Shape (LENS) and Laser Metal Deposition-powder (LIVID-p) methods. These processes generally provide for the rapid manufacture a three-dimensional object (e.g., an article, component, part, product, etc.) through the sequential formation of a multiplicity of thin unit layers. More specifically, layers of a powder material are laid down and irradiated with an energy beam (e.g., laser beam) so that particles of the powder material within each layer are sequentially sintered (fused) or melted to solidify the layer.
- Descriptions of laser sintering/melting technology can be found, for example, in U.S. Pat. No. 4,863,538, U.S. Pat. No. 5,017,753, U.S. Pat. No. 5,076,869, and U.S. Pat. No. 4,944,817, each of which are hereby incorporated herein by reference in its entirety. In these methods, a laser beam is used to selectively fuse a powder material by scanning cross-sections of the material in a bed. These cross-sections are scanned based on a three-dimensional description of the desired object. This description may be obtained from various sources such as, for example, a computer aided design (CAD) file, scan data, or some other source. Electron sintering/melting technology operates using similar principles, except that an electron beam is used in place of a laser beam to locally transfer energy to the powder material.
- Other examples of additive manufacturing processes that can utilize the titanium alloys described herein include wire-based AM processes (i.e., wire directed energy deposition methods, such as Laser Metal Deposition-wire (LMD-w) and Electron Beam Additive Manufacturing (EBAM®) methods). Such methods are described, for example, in U.S. Pat. No. 7,073,561, U.S. Pat. No. 6,143,378, and U.S. Pat. Appl. Pub. 2014/0061974, each of which are hereby incorporated herein by reference in its entirety.
- Methods of forming objects via additive manufacturing processes can comprise applying energy to a first quantity of a powdered titanium alloy described herein on a substrate so as to fuse particles of the powdered titanium alloy into a first layer on the substrate; and forming at least one additional layer on the first layer by applying energy to at least a second quantity of a powdered titanium alloy described herein on the first layer so as to fuse particles of the powdered titanium alloy into the at least one additional layer on the first layer, thereby forming the object. Applying energy can comprise contacting the powdered titanium alloy with a laser beam or an electron beam (depending upon the additive manufacturing process employed).
- Methods of forming objects via additive manufacturing processes can also comprise directing an energy beam and feeding a feedstock comprising a titanium alloy described herein to a feed point adjacent to a substrate, thereby forming a molten puddle; moving the feed point relative to the substrate, thereby advancing the molten puddle of presently fed feedstock and rapidly solidifying previously fed feedstock; and sequentially advancing the feed point within a predetermined geometric volume, thereby sequentially fusing the feedstock, by action of the advancing molten puddle, into a near net shape work piece built-up upon the substrate. In these methods, the feedstock can comprise, for example, a wire formed from a titanium alloy described herein.
- As discussed above, by utilizing the titanium alloys described herein, objects that possess an equiaxed grain structure can be formed using an additive manufacturing process (without subsequent treatment steps to eliminate a columnar grain structure). The term “equiaxed grain structure,” as used herein, refers to a grain structure that includes a population of grains having an average aspect ratio of 3:1 or less. Standard methods for determining the average grain size of grains present in a metal are known in the art. See, for example, ASTM E112-12, entitled “Standard Test Methods for Determining Average Grain Size,” which is hereby incorporated herein by reference in its entirety. The average aspect ratio of grains can be calculated from the grain dimensions obtained using ASTM E112-12.
- In some embodiments, the object can exhibit an average grain aspect ratio of less than 2.5:1 (e.g., less than 2.25:1, less than 2:1, less than 1.9:1, less than 1.8:1, less than 1.7:1, less than 1.6:1, less than 1.5:1, less than 1.4:1, less than 1.3:1, or less). In some embodiments, the object can exhibit an average grain aspect ratio of greater than 1:1 (e.g., at least 1.3:1, at least 1.4:1, at least 1.5:1, at least 1.6:1, at least 1.7:1, at least 1.8:1, at least 1.9:1, at least 2:1, or at least 2.25:1). In some embodiments, the object can exhibit an average grain aspect ratio of about 1:1.
- The object can exhibit an average grain aspect ratio ranging from any of the minimum values described above to any of the maximum values described above. For example, in some embodiments, the object can exhibit an average grain aspect ratio of from 1.5 to 2.25. In some embodiments, the standard deviation of the average grain aspect ratio can be less than 1.
- In some embodiments, the object comprises grains, and at least 85% (e.g., at least 90%, or at least 95%) of the grains have an aspect ratio of less than 3:1. In some embodiments, the object comprises grains, and at least 85% (e.g., at least 90%, or at least 95%) of the grains have an aspect ratio of less than 2.5:1. In some embodiments, the object comprises grains, and at least 85% (e.g., at least 90%, or at least 95%) of the grains have an aspect ratio of less than 2:1.
- Also provided herein are methods of forming titanium alloys for use in additive manufacturing. These methods can comprise combining a titanium material with a beta eutectoid stabilizer to form the titanium alloy. The beta eutectoid stabilizer can be added in an effective amount to produce an equiaxed grain structure when the titanium alloy is melted or sintered during an additive manufacturing process. In some embodiments, the method can further comprise micronizing the titanium alloy to form a population of particles suitable for use in an additive manufacturing process.
- By way of non-limiting illustration, examples of certain embodiments of the present disclosure are given below.
- Materials and Methods
- An Optomec Laser Engineered Net Shaping (LENS™) additive manufacturing device with two powder feeders was used to deposit single composition and compositionally graded cylinders using pre-alloyed and elemental powders. The pre-alloyed powders included commercially pure titanium (CP Ti), Ti-6Al-4V and Ti18 and the elemental powders were iron, nickel and copper. Custom elemental blend powders, made by mixing the pre-alloyed and elemental powders in the correct ratio for the desired composition, were also used. To deposit the compositional gradient, powder feeder one contained the pre-alloyed powder and powder feeder two contained the elemental blend. The rpm (flow rate control reference for The Ohio State University LENS™) of powder feeder one was set to three and the rpm of powder feeder two was set to zero. During the deposition, the rpm of powder feeder one was decreased while the rpm of powder feeder two was increased by the same amount. The rpm change was done in a stepwise function to create distinct composition layers. The laser power varied between 300 W and 325 W depending on the composition. The travel speed was set at 20″/min, the layer spacing was 0.010″ and the hatch width was 0.015″.
- After deposition, the specimens were sectioned parallel to the build direction and the plane parallel to the build direction was polished through 0.05 um colloidal silica. The as-deposited specimens were characterized using an FEI Apreo scanning electron microscope (SEM). Backscattered electron (BSE) images were acquired for grain analysis. X-ray energy dispersive spectroscopy (XEDS) was performed using an EDAX Octane Elect silicon-drift detector to determine the sample composition. A Hikari electron backscattered diffraction (EBSD) camera and OIM Data Collection 7.0 was used for acquiring grain orientation data. The orientation data was analyzed using OIM Data Analysis 8.0.
- To determine the grain aspect ratio, the individual grains were manually separated along the grain boundary alpha. If there was no grain boundary alpha present, a grain boundary map from the EBSD orientation data was used. Using the image analysis program MIPAR and its Feature Measurements tool, the major axis length and minor axis length of each grain was determined. The aspect ratio was calculated by dividing the major axis length by the minor axis length. All edge grains were removed from the image before quantification. The texture of the beta grains was calculated if more than half of the data points were the beta phase.
- Results and Discussion
- Additive manufacturing of CP Ti or conventions titanium alloys produces coarse columnar grains as seen in the as-deposited titanium alloy Ti18 (
FIGS. 1A and 1B ).FIG. 2A is an image quality (IQ) map of as-deposited Ti18. The IQ map is based on the pattern quality of the EBSD data. Lower pattern quality results in a lower IQ value and is therefore a darker point in the IQ map. Grain boundaries typically have low quality and therefore can be used for grain identification. The darker lines inFIG. 2A are the grain boundaries of the columnar grains.FIG. 2B is an inverse pole figure (IPF) map of the selected area. An IPF map shows the grain orientation relative to the sample normal, rolling or transverse direction. The pole figure (FIG. 2C ) shows the preferred orientation of the columnar grains with a times random value of 28.6. The times random value is the ratio of the actual measured grain orientation and a calculated truly random grain orientation. The higher the times random value, the greater the amount of texture in the build. - Ti18+Iron
- Builds was performed using Ti18 containing varying amounts of Fe. The resulting grain structures are shown in
FIGS. 3A and 3B . When low quantities of Fe were present, columnar grains were formed. The addition of increasing amounts of Fe to Ti18 produced an equiaxed grain structure along the build direction. - Electron-backscattered diffraction (EBSD) analysis was also performed on the Ti18 plus iron sample.
FIG. 4A is an image quality map showing the grain boundaries.FIG. 4B is an inverse pole figure (IPF) map of the selected area.FIG. 4C shows the pole figure (PF) of the scanned area with a times random value of 7.426, which is less than the Ti18 as-deposited times random value of 28.6. This indicates that the columnar structure has broken down upon the addition of iron, and an equiaxed structure has now formed. - The grain structure of an equiaxed region of the build was analyzed statistically. The results are included in the table below.
-
Aspect Ratio Above Above Above Above Total 3:1 4:1 5:1 6:1 Alloy Composition (wt %) Grains Average Grains Grains Grains Grains Ti Al Mo V Cr Fe Counted (St. Dev) (%) (%) (%) (%) Ti18 + 78.28 5.71 3.81 5.53 2.23 4.44 207 1.89 17 7 1 0 Fe (0.75) (8.2%) (3.4%) (0.5%) (0%) - Ti18+Copper and Ti18+Nickel
- Builds was performed using Ti18 containing varying amounts of Cu (see
FIG. 5 ). The addition of copper to Ti18 also promoted an equiaxed grain structure. A transition from equiaxed grains back to columnar grains can be seen near the top of the build at the transition from Ti18 plus copper to only Ti18. - A similar build was conducted using Ti18 containing varying amounts of Ni (see
FIG. 6A ).FIG. 6B shows a line drawing of the grain boundaries of a portion of a build including Ti18+2.41% by weight nickel. The structure appeared equiaxed. The grain structure of the region of the build was analyzed statistically. The results are included in the table below. -
Aspect Ratio Above Above Above Above Total 3:1 4:1 5:1 6:1 Alloy Composition (wt %) Grains Average Grains Grains Grains Grains Ti Al Mo V Cr Fe Ni Counted (St. Dev) (%) (%) (%) (%) Ti18 + 79.53 5.64 3.82 5.58 2.25 0.77 2.41 242 1.80 14 4 1 0 Ni (0.68) (5.8%) (1.7%) (0.4%) (0%) - Ti64+Beta Eutectoid Stabilizer
- Builds was performed using Ti64 containing varying amounts of a beta eutectoid stabilizer (Fe, Ni, or combinations thereof).
FIGS. 7A-7F show line drawings of the grain boundaries of portions of these builds. The grain structure of regions of these builds were analyzed statistically and were found to be equiaxed. The results are included in the table below. -
Aspect Ratio Above Above Above Above Total 3:1 4:1 5:1 6:1 Alloy Composition (wt %) Grains Average Grains Grains Grains Grains Ti Al V Fe Ni Counted (St. Dev) (%) (%) (%) (%) Ti64 + Ni 86.22 6.3 4 0 3.47 147 1.74 (0.69) 6 3 1 1 (4.1%) (2.0%) (0.7%) (0.7%) Ti64 + Ni 83.58 5.99 4.09 0 6.33 204 1.75 (0.66) 12 3 1 0 (5.9%) (1.5%) (0.5%) (0%) Ti64 + Fe 84.14 5.89 4.06 5.90 0 235 1.85 (1.01) 19 13 4 3 (8.1%) (5.5%) (1.7%) (1.3%) Ti64 + Fe 82.77 5.79 4.01 7.43 0 169 1.77 (0.63) 10 2 0 0 (5.9%) (1.2%) (0%) (0%) Ti64 + 83.96 6.06 4.18 3.52 2.27 133 1.80 (0.61) 6 1 0 0 Fe and Ni (4.5%) (0.8%) (0%) (0%) Ti64 + 81.59 5.93 4.12 5.30 3.06 126 1.93 (0.77) 12 5 1 0 Fe and Ni (9.5%) (4.0%) (0.8%) (0%) - CP Ti+Beta Eutectoid Stabilizer
- Builds was performed using CP Ti containing varying amounts of a beta eutectoid stabilizer (Fe or a combination of N).
FIGS. 8A-8C show line drawings of the grain boundaries of portions of these builds. The grain structure of regions of these builds were analyzed statistically and were found to be equiaxed. The results are included in the table below. -
Aspect Ratio Alloy Above Above Above Above Composition 3:1 4:1 5:1 6:1 (wt %) Total Grains Average Grains Grains Grains Grains Ti Fe Ni Counted (St. Dev) (%) (%) (%) (%) CP Ti + Fe 92.25 7.75 0 202 1.92 (0.84) 17 8 3 1 (8.4%) (4.0%) (1.5%) (0.5%) CP Ti + 93.65 4.35 2.0 168 2.00 (0.82) 19 6 1 0 Fe and Ni (11.3%) (3.6%) (0.6%) (0%) - The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims. Any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative compositions and method steps disclosed herein are specifically described, other combinations of the compositions and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein or less, however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated.
- The term “comprising” and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various embodiments, the terms “consisting essentially of” and “consisting of” can be used in place of “comprising” and “including” to provide for more specific embodiments of the invention and are also disclosed. Other than where noted, all numbers expressing geometries, dimensions, and so forth used in the specification and claims are to be understood at the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, to be construed in light of the number of significant digits and ordinary rounding approaches.
- Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of skill in the art to which the disclosed invention belongs. Publications cited herein and the materials for which they are cited are specifically incorporated by reference.
Claims (19)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/905,531 US20180245186A1 (en) | 2017-02-24 | 2018-02-26 | Titanium alloys for additive manufacturing |
US17/232,925 US20210238712A1 (en) | 2017-02-24 | 2021-04-16 | Titanium alloys for additive manufacturing |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201762463338P | 2017-02-24 | 2017-02-24 | |
US15/905,531 US20180245186A1 (en) | 2017-02-24 | 2018-02-26 | Titanium alloys for additive manufacturing |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US17/232,925 Division US20210238712A1 (en) | 2017-02-24 | 2021-04-16 | Titanium alloys for additive manufacturing |
Publications (1)
Publication Number | Publication Date |
---|---|
US20180245186A1 true US20180245186A1 (en) | 2018-08-30 |
Family
ID=63245661
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/905,531 Abandoned US20180245186A1 (en) | 2017-02-24 | 2018-02-26 | Titanium alloys for additive manufacturing |
US17/232,925 Pending US20210238712A1 (en) | 2017-02-24 | 2021-04-16 | Titanium alloys for additive manufacturing |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US17/232,925 Pending US20210238712A1 (en) | 2017-02-24 | 2021-04-16 | Titanium alloys for additive manufacturing |
Country Status (5)
Country | Link |
---|---|
US (2) | US20180245186A1 (en) |
EP (1) | EP3585914A4 (en) |
JP (1) | JP2020511597A (en) |
CA (1) | CA3054729A1 (en) |
WO (1) | WO2018157071A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110882414A (en) * | 2019-12-26 | 2020-03-17 | 中南大学 | Porous oral implant and preparation method thereof |
EP3685957A1 (en) * | 2019-01-28 | 2020-07-29 | Goodrich Corporation | Systems and methods for wire deposited additive manufacturing using titanium |
CN111992713A (en) * | 2020-07-16 | 2020-11-27 | 国营芜湖机械厂 | Selective laser melting forming method for aircraft air inlet protective grating |
CN112359249A (en) * | 2020-09-29 | 2021-02-12 | 中国科学院金属研究所 | Nanocrystalline Ti6Al4V-Cu alloy and additive manufacturing and preparation method thereof |
CN112593171A (en) * | 2020-12-09 | 2021-04-02 | 四川大学 | Fine-grained pure titanium with high toughness and excellent osseointegration performance and preparation method thereof |
US11786972B2 (en) | 2021-11-12 | 2023-10-17 | Goodrich Corporation | Systems and methods for high strength titanium rod additive manufacturing |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2577490B (en) | 2018-09-24 | 2022-03-02 | Alloyed Ltd | A beta titanium alloy for additive manufacturing |
CN110777283A (en) * | 2019-08-02 | 2020-02-11 | 宁波中星新材料研究院有限公司 | Titanium alloy for arc fuse additive manufacturing and preparation method thereof |
DE112020003981A5 (en) | 2019-08-22 | 2022-05-05 | BEGO Bremer Goldschlägerei Wilh. Herbst GmbH & Co.KG | Use of a titanium-iron alloy for the production of a metallic shaped dental body or a veneered dental restoration, corresponding metallic shaped dental bodies, veneered dental restorations and methods |
CN111069600B (en) * | 2019-12-17 | 2021-06-29 | 上海交通大学 | Additive manufacturing method of low-modulus titanium/titanium layered material |
CN113604695B (en) * | 2021-08-10 | 2022-01-07 | 内蒙古科技大学 | Method for optimizing additive manufacturing of titanium alloy structure by adding rare earth alloy |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060045789A1 (en) * | 2004-09-02 | 2006-03-02 | Coastcast Corporation | High strength low cost titanium and method for making same |
US20140116581A1 (en) * | 2011-04-29 | 2014-05-01 | Aktiebolaget Skf | Heat-Treatment of an Alloy for a Bearing Component |
US20170306450A1 (en) * | 2016-04-25 | 2017-10-26 | Arconic Inc. | Bcc materials of titanium, aluminum, niobium, vanadium, and molybdenum, and products made therefrom |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0790432A (en) * | 1993-09-21 | 1995-04-04 | Nippon Steel Corp | Ultralow-chlorine alpha+beta type sintered titanium alloy made of isometric structure |
JP5627935B2 (en) * | 2009-07-24 | 2014-11-19 | 山陽特殊製鋼株式会社 | Ti brazing filler metal |
US10119178B2 (en) * | 2012-01-12 | 2018-11-06 | Titanium Metals Corporation | Titanium alloy with improved properties |
RU2659524C2 (en) * | 2014-01-28 | 2018-07-02 | Титаниум Металс Корпорейшн | Titanium alloys exhibiting resistance to impact or shock loading and method of making a part therefrom |
US10442000B2 (en) * | 2015-03-05 | 2019-10-15 | Toho Titanium Co., Ltd. | Titanium-based powder, and ingot and sintered article thereof |
CN105522151B (en) * | 2016-01-19 | 2018-02-23 | 段瑞行 | A kind of method of 3D printing medical titanium alloy material |
JP7022698B2 (en) * | 2016-04-25 | 2022-02-18 | ハウメット エアロスペース インコーポレイテッド | BCC materials of titanium, aluminum, vanadium, and iron and products made from them |
CN106420119B (en) * | 2016-11-29 | 2017-10-31 | 淮阴工学院 | A kind of manufacturing process of high antibiotic property titanium alloy artificial hip joint |
-
2018
- 2018-02-26 JP JP2019546229A patent/JP2020511597A/en active Pending
- 2018-02-26 EP EP18758167.3A patent/EP3585914A4/en active Pending
- 2018-02-26 WO PCT/US2018/019749 patent/WO2018157071A1/en unknown
- 2018-02-26 CA CA3054729A patent/CA3054729A1/en active Pending
- 2018-02-26 US US15/905,531 patent/US20180245186A1/en not_active Abandoned
-
2021
- 2021-04-16 US US17/232,925 patent/US20210238712A1/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060045789A1 (en) * | 2004-09-02 | 2006-03-02 | Coastcast Corporation | High strength low cost titanium and method for making same |
US20140116581A1 (en) * | 2011-04-29 | 2014-05-01 | Aktiebolaget Skf | Heat-Treatment of an Alloy for a Bearing Component |
US20170306450A1 (en) * | 2016-04-25 | 2017-10-26 | Arconic Inc. | Bcc materials of titanium, aluminum, niobium, vanadium, and molybdenum, and products made therefrom |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3685957A1 (en) * | 2019-01-28 | 2020-07-29 | Goodrich Corporation | Systems and methods for wire deposited additive manufacturing using titanium |
US20200238379A1 (en) * | 2019-01-28 | 2020-07-30 | Goodrich Corporation | Systems and methods for wire deposited additive manufacturing using titanium |
US11819954B2 (en) * | 2019-01-28 | 2023-11-21 | Goodrich Corporation | Systems and methods for wire deposited additive manufacturing using titanium |
CN110882414A (en) * | 2019-12-26 | 2020-03-17 | 中南大学 | Porous oral implant and preparation method thereof |
CN111992713A (en) * | 2020-07-16 | 2020-11-27 | 国营芜湖机械厂 | Selective laser melting forming method for aircraft air inlet protective grating |
CN112359249A (en) * | 2020-09-29 | 2021-02-12 | 中国科学院金属研究所 | Nanocrystalline Ti6Al4V-Cu alloy and additive manufacturing and preparation method thereof |
CN112593171A (en) * | 2020-12-09 | 2021-04-02 | 四川大学 | Fine-grained pure titanium with high toughness and excellent osseointegration performance and preparation method thereof |
US11786972B2 (en) | 2021-11-12 | 2023-10-17 | Goodrich Corporation | Systems and methods for high strength titanium rod additive manufacturing |
Also Published As
Publication number | Publication date |
---|---|
JP2020511597A (en) | 2020-04-16 |
EP3585914A4 (en) | 2020-11-18 |
EP3585914A1 (en) | 2020-01-01 |
CA3054729A1 (en) | 2018-08-30 |
WO2018157071A1 (en) | 2018-08-30 |
US20210238712A1 (en) | 2021-08-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20210238712A1 (en) | Titanium alloys for additive manufacturing | |
EP3266541B1 (en) | Titanium powder | |
Wang et al. | Laser fabrication of Ti6Al4V/TiC composites using simultaneous powder and wire feed | |
CN113348262A (en) | Method for manufacturing aluminum alloy parts | |
JP7126504B2 (en) | Powders for use in additive manufacturing processes | |
CN105283569B (en) | Cermet and its manufacture method and cutting element | |
Gustmann et al. | Properties of a superelastic NiTi shape memory alloy using laser powder bed fusion and adaptive scanning strategies | |
US10094012B2 (en) | Ni-Ir-based heat-resistant alloy and process for producing same | |
CN107735504B (en) | Sputtering target material | |
Dikova et al. | Microstructure and hardness of fixed dental prostheses manufactured by additive technologies | |
JP2016172904A (en) | Granule for lamination molding, and method for producing the same | |
JP2017186653A (en) | Three-dimensional shape molded article and manufacturing method therefor | |
WO2020106764A1 (en) | Aluminum alloy products and methods for making the same | |
EP3411171B1 (en) | Method for producing a three-dimensional hard metal body in layers | |
Altug-Peduk et al. | Experimental investigation on the EBM-based additively manufactured prismatic nickel–titanium SMA components | |
JP6198062B2 (en) | Co-based alloy powder | |
Mergulhão et al. | Investigation of mechanical, microstructural and thermal behavior of CoCrMo alloy manufactured by selective laser melting and casting techniques | |
US11759857B2 (en) | Material obtained by compaction and densification of metallic powder(s) | |
Mendoza et al. | On the role of composition and processing parameters on the microstructure evolution of Ti-xMo alloys | |
JP7285112B2 (en) | Powder for modeling, method for producing this powder and method for producing shaped articles | |
JP6230885B2 (en) | α + β type titanium alloy and method for producing the same | |
JP7036413B2 (en) | Co-based alloy powder for electron beam laminated modeling | |
WO2020110498A1 (en) | Powder for laminate formation use, laminated article, and method for producing laminated article | |
Habibe et al. | Co-Cr-Mo-W powder obtained by mechanical alloying | |
JP2019099920A (en) | Methods and compositions for making near net shape article |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
AS | Assignment |
Owner name: OHIO STATE INNOVATION FOUNDATION, OHIO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WELK, BRIAN;FRASER, HAMISH;REEL/FRAME:046756/0610 Effective date: 20180307 |
|
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 |
|
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: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE AFTER FINAL ACTION FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |