WO2021211685A1 - Printable hard ferrous metallic alloys for additive manufacturing by direct energy deposition processes - Google Patents
Printable hard ferrous metallic alloys for additive manufacturing by direct energy deposition processes Download PDFInfo
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- WO2021211685A1 WO2021211685A1 PCT/US2021/027237 US2021027237W WO2021211685A1 WO 2021211685 A1 WO2021211685 A1 WO 2021211685A1 US 2021027237 W US2021027237 W US 2021027237W WO 2021211685 A1 WO2021211685 A1 WO 2021211685A1
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- metallic part
- mpa
- alloy
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- hardness
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Links
- 238000004519 manufacturing process Methods 0.000 title description 11
- 239000000654 additive Substances 0.000 title description 7
- 230000000996 additive effect Effects 0.000 title description 7
- 229910001092 metal group alloy Inorganic materials 0.000 title description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title description 4
- 238000005137 deposition process Methods 0.000 title description 2
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 83
- 239000000956 alloy Substances 0.000 claims abstract description 83
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 38
- 238000000151 deposition Methods 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 7
- 238000010276 construction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 238000005256 carbonitriding Methods 0.000 claims description 2
- 238000005255 carburizing Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000005121 nitriding Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000011572 manganese Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 238000010587 phase diagram Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000007639 printing Methods 0.000 description 7
- 238000010146 3D printing Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 229910000851 Alloy steel Inorganic materials 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910001566 austenite Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000734 martensite Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 238000000399 optical microscopy Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910000788 1018 steel Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910021652 non-ferrous alloy Inorganic materials 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009692 water atomization Methods 0.000 description 1
- 238000003963 x-ray microscopy Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
-
- 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/60—Treatment of workpieces or articles after build-up
- B22F10/62—Treatment of workpieces or articles after build-up by chemical means
-
- 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
- B22F10/60—Treatment of workpieces or articles after build-up
- B22F10/64—Treatment of workpieces or articles after build-up by thermal means
-
- 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
-
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
-
- 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
- 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
- B33Y80/00—Products made by additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
- C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
-
- 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
-
- 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
- B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
- B22F12/10—Auxiliary heating means
- B22F12/17—Auxiliary heating means to heat the build chamber or platform
-
- 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
- B22F2301/35—Iron
-
- 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
- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- 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
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- 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
- the application is directed at ferrous alloy compositions that produce metallic parts using direct energy deposition additive manufacturing or 3D printing methods.
- Additive manufacturing also known as 3D printing, typically involves the layer-by- layer deposition of the material to “build” or “print” a part in three dimensions. Manufacturing in this way has numerous advantages over traditional subtractive methods, including the ability to produce complex geometries otherwise not possible to manufacture, rapid part production times, and material cost savings.
- DED directed energy deposition
- DLD direct laser deposition
- LENS laser engineer net shaping
- DMD direct metal deposition
- SMD shaped metal deposition
- LMD laser metal deposition
- ferrous alloy compositions are provided that produce metallic parts with relatively high hardness, strength, and/or ductility when made using direct energy deposition additive manufacturing or 3D printing methods. These properties are achieved by formulating the chemistries of these alloys to develop phases and microstructures in the presence of processing conditions (i.e. times and temperatures) experienced in the direct energy deposition process.
- a method of layer-by-layer construction of a part by direct energy deposition is provided.
- An alloy is supplied in powder, or particle form with the composition of Fe at 69.2 wt.% to 89.1 wt.%; Cr at 7.25 wt.% to 16.0 wt.%; Nb at 0.01 wt.% to 10.0 wt.%; Mo at 0.5 wt.% to 4.0 wt.%; C at 0.03 wt. % to 0.4 wt.
- the metallic part has a tensile strength of at least 1300 MPa, a yield strength of at least 700 MPa, a elongation of at least 4.0%, and a hardness of at least 45 HRC.
- Ni, Cu, Si, W, Mn, N and B are optional and if present, fall in the following range: Ni (1.5 wt.% to 4.0 wt. %), Cu (0.1 wt. % to 3.0 wt. %), Si (0.1 wt. % to 1.0 wt. %), W (0.1 wt. % to 6.0 wt. %), Mn (0.4 wt % to 1.9 wt. %), N (0.03 wt. % to 1.0 wt. %) and B (0.01 wt. % to 0.05 wt. %).
- layers having a thickness in the range of 20 microns to 1000 microns thick layers are provided.
- the metal may be deposited at a rate typically around from 0.5 kg/hr to 10 kg/hr.
- a printed metallic part has the composition of Fe at 69.2 wt.% to 89.1 wt.%; Cr at 7.25 wt.% to 16.0 wt.%; Nb at 0.01 wt.% to 10.0 wt.%; Mo at 0.5 wt.% to 4.0 wt.%. C at 0.03 wt. % to 0.4 wt. % and optionally one or more of Ni, Cu, Si, W, Mn, N and B.
- the printed metallic part has a tensile strength of at least 1300 MPa, a yield strength of at least 700 MPa, an elongation of at least 4.0%, and a hardness of at least 45 HRC.
- the printed metallic part has a tensile strength of at least 1300 MPa and up to 2200 MPa, a yield strength of at least 700 MPa and up to 1500 MPa, an elongation of at least 4 % and up to 20%, and a hardness of at least 45 HRC and up to 58 HRC.
- the alloy has Fe at 82.0 wt.% to 87.0 wt.%; Cr at
- the alloy has Fe at 82.0 wt.% to 87.0 wt.%; Cr at
- the alloy has Fe at 79.0 wt.% to 83.0 wt.%; Cr at
- the alloy has Fe 79.0 wt.% to 83.0 wt.%; Cr at 7.7 wt.% to 9.0 wt.%; Ni at 1.5 wt.% to 2.5 wt.%; Nb at 0.04 wt.% to 0.08 wt.%; Mo at 1.2 wt.% to 1.8 wt.%; W at 4.1 wt.% to 5.5 wt.%; Mn at 0.4 wt.% to 1.1 wt.%; C at 0.15 wt.% to 0.22 wt.%; N at 0.05 wt.% to 0.13 wt.%; and B at 0.01 wt.% to 0.05 wt.%.
- FIG. 1 is an optical microscopy micrograph of as-built alloy A1 built by
- FIG. 2 is an optical microscopy micrograph of as-built alloy A1 built by
- OPTOMEC® LENS TM 850-R after etching to reveal the micro structure.
- FIG. 3 is a scanning electron microscopy (SEM) micrograph of as-built alloy A1 built by OPTOMEC® LENS TM 850-R ) after etching to reveal the micro structure.
- FIG. 4 is an X-ray diffraction spectrum for as-built alloy A1 built by OPTOMEC®
- FIG. 5 is an equilibrium phase diagram for alloy A1 calculated using Thermo-Calc software.
- FIG. 6 is an equilibrium phase diagram for alloy A2 calculated using Thermo-Calc software.
- FIG. 7 is an equilibrium phase diagram for alloy A3 calculated using Thermo-Calc software.
- FIG. 8 is an equilibrium phase diagram for alloy A4 calculated using Thermo-Calc software.
- Directed energy deposition (DED) process for metal 3D printing may use a feed nozzle to propel powder into an energy source. This allows DED to manufacture relatively large-size products with higher printing speeds than additive manufacturing processes that use a powder bed. Besides high productivity, advantages of DED may include the ability to clad or repair previously produced parts as well as to create multi-material components.
- DED processes also may utilize certain conditions during processing, such as sustained baseline elevated temperatures, periodic thermal excursions, and rapid cooling rates that can be leveraged to form and develop desirable phases and microstructures that result in unique properties. While historically wrought or cast steel alloys can be used in DED systems, including 316L, 17-4PH, H13, and M300, they were not developed with the DED processes in mind. Therefore, there are opportunities to develop new steel alloy compositions specifically for DED that can achieve mechanical properties similar to or better than current wrought or cast alloys.
- the present application discloses metal alloy compositions that exhibit a combination of printability by direct energy deposition (DED) methods and mechanical properties.
- the metal alloy compositions may have a relatively high hardness (between 45 HRC and 58 HRC), relatively high strength (yield between 700 MPa and 1500 MPa, tensile between 1300 MPa and 2200 MPa) , and/or relatively high ductility (between 4% and 20% elongation) in the “as-built” state.
- printability herein refers to the ability to print a metal alloy on a DED machine.
- the printing is such that it may occur without defects that would compromise the use of the printed part for a given application, such as cracking and porosity, without imposing conditions that encumber the process, such as elevating process temperature or time.
- the “as-built” condition is defined as that produced by the DED machine and may be without any post-printing processing that manipulates the microstructure, such as heat treating.
- the “heat treated” condition refers to the state of the printed metal after it has been exposed to a thermal process designed to alter the microstructure to achieve certain properties.
- the present disclosure relates to alloys containing the following concentrations of elements: Fe at 69.2 wt.% to 89.1 wt.%, Cr at 7.2 wt.% to 16.0 wt.%, Ni up to 4.0 wt.%, Nb at 0.01 wt.% to 10.0 wt.%, Cu up to 3.0 wt.%, Mo at 0.5 wt.% to 4.0 wt.%, Si up to 1.0 wt.%, W up to 6.0 wt.%, Mn up to 1.9 wt.%, C at 0.03 wt.% to 0.4 wt.%, N up to 1.0 wt.%, and B up to 0.25 wt.%.
- Ni, Cu, Si, W, Mn, N and B are optional and if present, may fall in the following range: Ni (1.5 wt.% to 4.0 wt. %), Cu (0.1 wt. % to 3.0 wt. %), Si (0.1 wt. % to 1.0 wt. %), W (0.1 wt. % to 6.0 wt. %), Mn (0.4 wt % to 1.9 wt. %), N (0.03 wt. % to 1.0 wt. %) and B (0.01 wt. % to 0.05 wt. %).
- the alloys are free of Co for low environmental, health and safety (EH&S) risk. That is, the level of Co may be less than 0.1 wt.%. In another embodiment, the level is less than 0.05 wt.%.
- Some embodiments may not contain Tungsten (W), Manganese (Mn) or Boron (B). Some embodiments contain W; some embodiments contain Mn; some embodiments contain both W and Mn; and some embodiments contain B.
- the alloys may be supplied for the DED process in particle form made from conventional methods.
- the particles are may be produced using gas or water atomization processes with either nitrogen or argon gas for the former.
- the particles may have a diameter in the range of 1 micron to 500 microns. In another embodiment, the particles may have a diameter in the range of 10 microns to 300 microns. In a further embodiment, the particles may have a diameter in the range of 45 microns to 250 microns.
- DED parts are may be built from the metal alloys herein using commercially available DED machines such as the OPTOMEC® LENS TM 850-R.
- the parts may be built in an inert atmosphere, such as in argon gas.
- Parts may be built on a substrate that is preheated up to 800°C.
- the substrate may be preheated in the range of 50°C to 200°C.
- the substrate may be preheated in the range of in the range of 50°C to 100°C.
- no preheating of the substrate can be employed.
- the metal substrate may be composed of 1018 steel. However, it is contemplated that other steel and non-ferrous alloys can be used as substrates.
- the DED procedure herein contemplates a build-up of individual layers of the alloys each having a thickness 20 microns and higher.
- the individual layers of alloys each have a thickness in the range of 20 to 2000 microns.
- the individual layers of alloys each have a thickness in the range of 40 to 1000 microns.
- the individual layers of alloys each have a thickness in the range of 100 to 800 microns.
- the beam diameter may be in the range of 0.1 mm to 50 mm. In another embodiment, the beam diameter may be in the range of 0.4 mm to 10 mm. In another embodiment, the beam diameter may be in the range of 0.6 mm to 4 mm.
- the write speed of the printing nozzle may have a speed in the range of 2.5 to 250 cm/min. In another embodiment, the printing nozzle has a write speed in the range of 50 to 150 cm/min. In another embodiment, the printing nozzle has a write speed in the range of 75 to 105 cm/min.
- the method of construction involves deposition by melting the metal powder in an atmosphere with less than or equal to 50 ppm oxygen content.
- the atmosphere may be less than or equal to 40 ppm oxygen content, or ⁇ 30 ppm oxygen, or ⁇ 20 ppm oxygen, or ⁇ 10 ppm oxygen, or ⁇ 5 ppm oxygen, or ⁇ 1.0 ppm oxygen and directing it to a specified location on a substrate at room temperature or preheated between 50 °C to 800 °C where it solidifies.
- the level of oxygen may be in the range of 0.1 ppm to 50 ppm.
- the level of oxygen may be in the range of 0.1 ppm to 10 ppm.
- the level of oxygen may be in the range of 0.1 ppm to 5.0 ppm.
- the level of oxygen may be in the range of 0.1 ppm to 2.5 ppm.
- the average porosity in a part may be less than 1.0%. In another embodiment, the average porosity in a part may be less than 0.5%. In another embodiment, the average porosity in a part may be less than 0.3%. Low porosity and no cracking in as-built parts with the metals alloys described herein is evidenced in the cross-section optical micrograph image shown in Error! Reference source not found., which is of a part made with alloy A1 by the OPTOMEC® LENS TM 850-R.
- This part is made to a height of 25 mm using 0.5 mm to 1 mm thick layers on a 1018 steel substrate with no pre-heating.
- the average porosity is 0.22% as measured per ASTM E1245-03 (2016), which involves optical image analysis of a micrographic taken at 50x of a metallographic cross-section of the part.
- Table 2 shows the mechanical properties of as-built parts produced from traditional commercial steel alloys in comparison to the alloys Al, A2, A3, and A4 described herein in Table 1 using DED. Properties of alloys Al, A2, A3, and A4 were measured on parts built using a OPTOMEC® LENS TM 850-R built on a 1018 substrate with no preheating to height of 25 mm, using 0.5-1 mm layers. It is to be appreciated that alloy Al described herein exhibits yield and tensile strengths that exceed those of currently available steels also built using DED, including 316L, M300, 17-4 PH, and H13. Furthermore, that alloy Al has a combination of high strength and elongation (i.e. ductility) that is not present in the currently available steels.
- alloys described herein in the as-built condition have a high tensile strength of at least 1300 MPa.
- the alloys in the as-built condition may have a tensile strength of at least 1500 MPa.
- the alloys in the as-built condition may have a tensile strength of at least 1600 MPa.
- the alloys in the as-built condition may have a tensile strength in the range of 1300 MPa to 2200 MPa.
- the alloys in the as-built condition may have a tensile strength in the range of 1600 MPa to 2100 MPa.
- the alloys achieve a high tensile strength in combination with a high yield strength.
- the yield strength is at least 700 MPa. In another embodiment, the yield strength is at least at least 900 MPa. In another embodiment, the alloys may have a yield strength in the range of 700 MPa to 1500 MPa.
- tensile and yield strengths are also achieved in combination with elongation of at least 4%.
- the elongation may be at least 5%.
- the elongation may be in the range of 4% to 20%.
- the elongation may be in the range of 4% to 17%.
- This tensile strength, yield strength, and elongation are also achieved in combination with a hardness (HRC) of at least 45 HRC.
- the hardness may be at least 50 HRC.
- the hardness may be in the range of 45 HRC to 58 HRC.
- it contemplated herein that hardness herein may be in the range of 50 HRC to 58 HRC.
- the alloys herein are such that they can have a tensile strength of at least 1300 MPa, a yield strength of at least 700 MPa, an elongation of at least 4%, and a hardness of at least 45 HRC.
- Other combinations of tensile strength, yield strength, elongation and hardness may be realized in as-built parts from the individual preferred levels of tensile strength, yield strength, elongation, and hardness.
- Table 2 illustrates the alloys according to the present invention having high yield and tensile strength and hardness.
- the metallic part of alloy A1 has tensile strength of at least 1400 MPa.
- the alloy A1 may have yield strength of at least 1000 MPa.
- the alloy A1 may have elongation of at least 10.0%.
- the alloy A1 may have hardness of at least 46 HRC.
- the metallic part of alloy A2 has tensile strength of at least 1300 MPa.
- the alloy A2 may have yield strength of at least 800 MPa.
- the alloy A2 may have elongation of at least 4%.
- the alloy A2 may have hardness of at least 46 HRC.
- the metallic part of alloy A3 has tensile strength of at least 1600 MPa.
- the alloy A3 may have yield strength of at least 700 MPa.
- the alloy A3 may have elongation of at least 6%.
- the alloy A3 may have hardness of at least 48 HRC.
- the metallic part of alloy A4 has tensile strength of at least 1700 MPa.
- the alloy A4 may have yield strength of at least 700 MPa.
- the alloy A4 may have elongation of at least 8%.
- the alloy A4 may have hardness of at least 49 HRC.
- X-ray diffraction (XRD) spectrum of a part made from alloy A1 seen in FIG. 4 is evidence of the presence of martensite/ferrite (BCC) and austenite (FCC) phases in the as-built structure.
- the X-ray diffraction spectrum was collected using a Bruker D5000 X-ray diffractometer with Cu Ka radiation. Martensite/ferrite and austenite are also observed in micrographs of the microstructure collected by optical and scanning electron microscopy (SEM) as seen in FIG. 2 and FIG. 3, respectively.
- the part was built using a by the OPTOMEC® LENS TM 850-R built on a 1018 substrate with no preheating to height of 25 mm, using 0.5-1 mm layers.
- FIG. 5 is an equilibrium phase diagram of alloy A1 generated by Thermo-Calc software (Thermo-Calc Software, Inc., version 2018b, TCFE9: TCS Steels/Fe-alloys Database, v9). Consistent with the XRD and microscopy data, the phase diagram predicts the primary phases in the structure are preferably of body centered cubic (BCC) and face centered cubic (FCC) phases. Also predicted are several secondary phases that are contemplated to form during solidification and/or during repetitive heating cycles from deposition of subsequent and adjacent layers during the printing process. These phases are predicted by the phase diagram to be various carbides, nitrides, and carbonitrides.
- BCC body centered cubic
- FCC face centered cubic
- the combination of the primary and secondary phases contribute to the measured high strength, hardness, and ductility (e.g. elongation) of alloys Al, A2, A3, and A4 described herein compared to currently available steel alloys for DED processes.
- the phases are governed by the chemistry and the processing conditions specific to the DED processes.
- these alloys can be heat treated by conventional quench and temper processes to enhance and/or alter the properties.
- heating the alloys to 1000 °C or above, but below the solidus temperature results in dissolution of more than 99% (mol faction), if not all of the secondary phases and the formation of austenite phase (FCC).
- FCC austenite phase
- quench and temper processes this is known as solutionizing or austenitizing the alloy.
- the alloy is quenched, or cooled rapidly, to room temperature in order to facilitate the conversion of austenite into martensite and prevent or limit the formation of secondary phases.
- the alloy can then be heated to temperatures between room and solutionizing temperatures to reduce residual stress as well as to form select secondary phases and grow these phases to certain sizes to optimize a desired property, a step known as tempering or aging.
- these alloys can undergo surface treatments such as nitriding, carburizing, and carbonitriding or that coatings can be applied by conventional methods such as physical vapor deposition (PVD), chemical vapor deposition (CVD), and plasma.
- PVD physical vapor deposition
- CVD chemical vapor deposition
- plasma plasma
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Abstract
Description
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US17/919,102 US20230166330A1 (en) | 2020-04-14 | 2021-04-14 | Printable hard ferrous metallic alloys for additive manufacturing by direct energy deposition processes |
CA3175537A CA3175537A1 (en) | 2020-04-14 | 2021-04-14 | Printable hard ferrous metallic alloys for additive manufacturing by direct energy deposition processes |
AU2021257835A AU2021257835A1 (en) | 2020-04-14 | 2021-04-14 | Printable hard ferrous metallic alloys for additive manufacturing by direct energy deposition processes |
JP2022562907A JP2023521915A (en) | 2020-04-14 | 2021-04-14 | Printable Hard Iron Metal Alloys for Additive Manufacturing by Direct Energy Deposition Process |
EP21787891.7A EP4135922A4 (en) | 2020-04-14 | 2021-04-14 | Printable hard ferrous metallic alloys for additive manufacturing by direct energy deposition processes |
CN202180028912.8A CN115605306A (en) | 2020-04-14 | 2021-04-14 | Printable hard ferrous metal alloy additively manufactured by direct energy deposition method |
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US20150328680A1 (en) * | 2014-05-16 | 2015-11-19 | The Nanosteel Company, Inc. | Layered Construction of Metallic Materials |
US20170021415A1 (en) * | 2015-07-21 | 2017-01-26 | Ansaldo Energia Ip Uk Limited | High temperature nickel-base superalloy for use in powder based manufacturing process |
US20170312857A1 (en) * | 2016-05-02 | 2017-11-02 | Board Of Regents, The University Of Texas System | Methods of additive manufacturing |
US20180312946A1 (en) * | 2014-11-03 | 2018-11-01 | Nuovo Pignone Srl | Metal alloy for additive manufacturing of machine components |
JP2020509152A (en) * | 2016-11-01 | 2020-03-26 | ザ・ナノスティール・カンパニー・インコーポレーテッド | 3D printable hard ferrous metal alloy for powder bed fusion |
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US8479700B2 (en) * | 2010-01-05 | 2013-07-09 | L. E. Jones Company | Iron-chromium alloy with improved compressive yield strength and method of making and use thereof |
SG11201803697SA (en) * | 2015-11-06 | 2018-06-28 | Innomaq 21 S L | Method for the economic manufacturing of metallic parts |
JP6985940B2 (en) * | 2018-01-09 | 2021-12-22 | 山陽特殊製鋼株式会社 | Stainless steel powder for modeling |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150328680A1 (en) * | 2014-05-16 | 2015-11-19 | The Nanosteel Company, Inc. | Layered Construction of Metallic Materials |
US20180312946A1 (en) * | 2014-11-03 | 2018-11-01 | Nuovo Pignone Srl | Metal alloy for additive manufacturing of machine components |
US20170021415A1 (en) * | 2015-07-21 | 2017-01-26 | Ansaldo Energia Ip Uk Limited | High temperature nickel-base superalloy for use in powder based manufacturing process |
US20170312857A1 (en) * | 2016-05-02 | 2017-11-02 | Board Of Regents, The University Of Texas System | Methods of additive manufacturing |
JP2020509152A (en) * | 2016-11-01 | 2020-03-26 | ザ・ナノスティール・カンパニー・インコーポレーテッド | 3D printable hard ferrous metal alloy for powder bed fusion |
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EP4135922A1 (en) | 2023-02-22 |
JP2023521915A (en) | 2023-05-25 |
CN115605306A (en) | 2023-01-13 |
US20230166330A1 (en) | 2023-06-01 |
EP4135922A4 (en) | 2024-04-17 |
CA3175537A1 (en) | 2021-10-21 |
AU2021257835A1 (en) | 2022-12-15 |
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