US20230392243A2 - Method for the additive manufacturing of an object from a maraging steel powder - Google Patents
Method for the additive manufacturing of an object from a maraging steel powder Download PDFInfo
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- US20230392243A2 US20230392243A2 US16/956,731 US201816956731A US2023392243A2 US 20230392243 A2 US20230392243 A2 US 20230392243A2 US 201816956731 A US201816956731 A US 201816956731A US 2023392243 A2 US2023392243 A2 US 2023392243A2
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 229910001240 Maraging steel Inorganic materials 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 19
- 239000000654 additive Substances 0.000 title claims description 11
- 230000000996 additive effect Effects 0.000 title claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 51
- 239000010959 steel Substances 0.000 claims abstract description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 238000003723 Smelting Methods 0.000 claims abstract 4
- 230000032683 aging Effects 0.000 claims description 29
- 229910001566 austenite Inorganic materials 0.000 claims description 25
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000000110 selective laser sintering Methods 0.000 claims description 6
- 238000010894 electron beam technology Methods 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims 2
- 238000000137 annealing Methods 0.000 abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 38
- 229910045601 alloy Inorganic materials 0.000 description 31
- 239000000956 alloy Substances 0.000 description 31
- 238000001556 precipitation Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000010936 titanium Substances 0.000 description 16
- 239000011651 chromium Substances 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910000734 martensite Inorganic materials 0.000 description 12
- 229910052719 titanium Inorganic materials 0.000 description 11
- 239000011572 manganese Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 229910000859 α-Fe Inorganic materials 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 238000005275 alloying Methods 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000001247 metal acetylides Chemical class 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010313 vacuum arc remelting Methods 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910001214 P-type tool steel Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000009689 gas atomisation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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- 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
-
- 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
- B22F10/10—Formation of a green body
- B22F10/14—Formation of a green body by jetting of binder onto a bed of metal powder
-
- 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
- B22F10/60—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
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/02—Hardening by precipitation
-
- 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
- C22C38/02—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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- 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
-
- 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
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
-
- 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
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
-
- 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 present invention relates to a method for producing a maraging steel according to the preamble to claim 1 .
- So-called maraging steels are steels whose alloy is virtually carbon-free.
- the maraging steels on the one hand, have high strength and on the other, have good toughness along with good processing and welding properties. They are used as tool steels for use at elevated temperatures, e.g. with intricately shaped die-cast or injection-molded plastic tools and for producing knives and blades for the sport of fencing.
- maraging steels are the hot-working steels 1.2709 and 1.6356.
- DE 603 19 197 T2 has disclosed a maraging steel, which contains at most 0.01% C, 8 to 22% nickel, 5 to 20% cobalt, 2 to 9% molybdenum, between 0 and 2% titanium, at most 1.7% aluminum, between 0 and 10 ppm magnesium, less than 10 ppm oxygen, less than 15 ppm nitrogen, and the rest iron and random impurities; this maraging steel contains nitride inclusions with a maximum length of 15 ⁇ m and oxide inclusions with a maximum length of 20 ⁇ m; the oxide inclusions include spinel-type inclusions and aluminum oxide inclusions, and in the total content of spinel-type inclusions with a length of at least 10 ⁇ m and Al 2 O 3 with a length of 10 ⁇ m, the percentage of spinel-type inclusions with a length of at least 10 ⁇ m is greater than 0.33. The intent of this is to take into account the objective of significantly reducing the non-metallic inclusions.
- EP 1 222 317 B1 has disclosed a high-strength, stainless machining steel; it is produced by powder metallurgy and should contain a precipitation-hardenable stainless steel alloy; this alloy contains at most 0.03% carbon, at most 1% manganese, at most 0.75% silicon, at most 0.04% phosphorus, 0.01 to 0.05% sulfur, 10 to 14% chromium, 6 to 12% nickel, at most 6% molybdenum, at most 4% copper, 0.4 to 2.5% titanium, and other minor alloy additives; the rest should be composed of iron and the usual impurities; a powder metallurgy product is to be produced from this, which should contain a fine dispersion of tiny sulfide particles whose major dimension is no greater than about 5 ⁇ m. It can also be used to produce a wire.
- EP 0 607 263 B1 has disclosed a precipitation-hardenable martensitic steel, which in addition to the usual small amounts of metals added to the alloy, also contains 10 to 14% chromium, 7 to 11% nickel, 2.5 to 6% molybdenum, and 0.5 to 4% copper; in this case, it can also contain up to 9% cobalt, the rest consisting of iron and the usual impurities.
- EP 2 631 432 B1 has disclosed a steam turbine rotor, a corresponding steam turbine, and a turbine power plant;
- the steam turbine rotor is a steam turbine low-pressure last stage long blade, which is composed of a precipitation-hardenable martensitic stainless steel, which contains less than 0.1% carbon and 9 to 14% chromium as well as 9 to 14% nickel, 0.5 to 2.5% molybdenum, and 0.5% or less silicon.
- additive production processes have already become very widespread in the industrial sector.
- additive production processes enjoy very widespread use today.
- Additive production processes are production processes in which printing data are generated by means of CAD data or from CAD data and articles can be printed, for example from plastics, using suitable printers.
- Such processes are also referred to as generative production processes.
- Suitable powder bed processes include selective laser melting (SLM), selective laser sintering (SLS), selective heat sintering (SHS), binder jetting, and electron beam melting (EBM).
- SLM selective laser melting
- SLS selective laser sintering
- SHS selective heat sintering
- EBM electron beam melting
- a powder bed is produced and in the regions in which an article is to be produced out of metal, energy is introduced with the corresponding means (laser or electron beam), which selectively melts the powder of the powder bed in that region. After the melting, another powder layer is applied and is in turn melted. The melting bonds this melted powder layer to the underlying powder layer, which has already been melted and solidified again or which is still in the molten phase, so that an article can be produced layer by layer, so to speak.
- the corresponding means laser or electron beam
- the object of the invention is to create a method for producing an article out of a maraging steel, which enables an optimal ratio of hardness to toughness.
- Another object is to produce an article out of a maraging steel, which has an optimal ratio of hardness to toughness.
- Another object is to produce a steel powder for use in an additive production process, which produces an article with an optimal ratio of hardness to toughness.
- a metal powder produced using the alloy concept according to the invention is printable and exhibits the required mechanical values after the aging alone so that an additional, usually required solution annealing step can be eliminated.
- an alloy concept is used, which is essentially based on nickel, aluminum, titanium, and silicon as hardening elements.
- the focus was placed on two points, namely on the one hand, increasing the hardness and strength values by modifying precipitation densities and types.
- the content of the precipitation-promoting elements aluminum and titanium was increased.
- FIG. 1 shows the influence of the titanium content
- FIG. 2 shows the influence of the molybdenum content
- FIG. 3 shows a time/temperature diagram of a heat treatment, which consists of a solution and washing procedure followed by an air-cooling to room temperature and an aging process.
- FIG. 4 shows the phase diagram of iron/nickel in equilibrium
- FIG. 5 shows the hysteresis of conversion temperatures of martensite and austenite 20 during heating and cooling
- FIG. 6 shows the hardness as a function of the aging temperature for different alloys
- FIG. 7 shows the austenite content as a function of the aging temperature for different alloys
- FIG. 8 shows the hardness curve as a function of the aging temperature in a printed, aged material according to the invention and in a solution annealed, aged material.
- Nickel is the most important alloying element in maraging steels. Since the carbon content is low in maraging alloys, the addition of Ni to Fe results in the formation of a cubic Fe—Ni martensite. Controlling the Ni content is also important because Ni is an austenite-stabilizing element and Ni is thus decisive for the formation of retransformed austenite. Ni forms intermetallic precipitations with numerous elements such as Al, Ti, and Mn and therefore plays an additional decisive role as a precipitation-promoting element.
- Aluminum is added to maraging steels as a precipitation element. It increases the solid solution strengthening and, particularly with Ni, forms intermetallic precipitations. A higher Al content can lead to the presence of ⁇ ferrite in the microstructure, which has a negative impact on the mechanical properties and on the corrosion resistance.
- Titanium appears to be one of the most active elements in maraging steels. It precipitates out during the aging and can be considered the most important alloying element for the formation of precipitations in maraging steels. It was used as a precipitation-promoting element in the first maraging steels that were developed and is used today in complex alloying systems.
- the greatest advantage is the rapid precipitation; titanium is thus much more active, for example, than Mo in C-type and T-type maraging steels in the early stages of precipitation.
- the enormous influence of the Ti content on the tensile strength 18% Ni and Co-containing maraging steels is shown in FIG. 1 .
- small quantities of Ti are added to Ti-free maraging steels in order to form carbides.
- the objective is to bind to the carbon C so that no other precipitation elements can form carbides.
- the influence of the Ti content is shown in FIG. 1 .
- Mo forms intermetallic compounds with Ni.
- the precipitation behavior of Mo is strongly influenced by other elements, especially by cobalt (Co), among others.
- Co cobalt
- the addition of Co decreases the solubility of Mo in the matrix and Mo is also forced to form precipitations. This leads to an increase in the hardness ( FIG. 2 ).
- Mo also increases the solid solution strengthening ( FIG. 2 ) and improves the corrosion resistance of high Cr-containing maraging steels.
- Chromium is added to improve the corrosion resistance of maraging steels. This yields steels that can be used, for example, as plastic mold steels, which are exposed to a chemical attack during the production of plastics.
- the addition of Cr to the alloy promotes the precipitation of the Laves phase. But higher Cr contents can lead to the formation of the ⁇ phase, which has a negative effect on the mechanical properties.
- spinodal segregation into Fe-rich and Cr-rich phases can occur, which reduces the notch impact strength.
- Mn was sometimes used to replace the more expensive Ni. Consistent with Ni, Mn forms a Mn martensite, but has less of an austenite-stabilizing effect and thus a significant quantity of ⁇ ferrite is present in Fe—Mn alloys. This b ferrite has a negative effect on the mechanical properties and on the corrosion resistance.
- Carbon is not an alloying element of a maraging steel. Because maraging steels cannot obtain their high strength from carbides, the carbon content is kept as low as possible during the production of the steel. For this reason, the carbon content of a maraging steel is in the range of 1/100%.
- Cu acts as a precipitation-promoting element in maraging steels; it does not, however, form a compound with other elements. At the beginning, it precipitates out with a cubic, body-centered structure in the Fe matrix. During the aging, it develops a 9R structure and in the end, it forms its cubic face-centered structure in equilibrium. The role of copper is to rapidly precipitate out and serve as a nucleation site for other precipitations.
- Silicon is usually considered an impurity element in steels. But in maraging steels, Si forms intermetallic phases and particularly in alloys that contain Ti, it forms the so-called Ni16Si7Ti6 G phase.
- G phase is used because the phase was discovered for the first time at grain boundaries; this is not the case, however, in maraging steels.
- the good mechanical properties of maraging steels can be attributed to a two-stage heat treatment.
- FIG. 3 shows an example of a time/temperature plan of such a heat treatment, which consists of a solution annealing procedure followed by an air-cooling to room temperature and an aging process.
- Ni-martensite is formed, which can be easily machined and cold-worked if need be.
- the subsequent aging is typically carried out in a temperature range of 400° C. to 600° C. During the aging process, three reactions occur:
- the phase diagram of Fe—Ni in equilibrium is shown in FIG. 4 . It clearly shows that Ni decreases the conversion temperature from austenite to ferrite and that in the alloys that contain more than a few percent Ni, the structure in equilibrium at room temperature consists of austenite and ferrite.
- the material does not decompose into a composition of austenite and ferrite in equilibrium. Instead, the austenite, with further cooling, is transformed into a cubic martensite.
- the aging of the martensitic structure is possible due to the influence of Ni in maraging steels, which leads to a hysteresis of the conversion temperatures of martensite and austenite during the heating and cooling ( FIG. 5 ). With an increasing Ni content, the conversion temperature of heating and cooling decreases. In this connection, the difference between the conversion temperatures depends on the Ni content.
- the material After the solution annealing, the material is transformed to a martensite if it is cooled to below the conversion temperature. Depending on the Ni content and the other alloying elements, a certain percentage of austenite can be retransformed at room temperature. If the microstructure is reheated again to below the ⁇ - ⁇ conversion temperature, then the martensite decomposes into an equilibrium structure composed austenite and ferrite. The speed of this reconversion reaction depends on the temperature used. Fortunately in maraging steels, this conversion is slow enough that precipitations of the intermetallic phases from the oversaturated solution form before the reconversion reaction dominates.
- the alloy is heated to above the ⁇ - ⁇ conversion temperature, then the martensite is retransformed due to annealing processes.
- the alloy concept according to the invention is essentially based on a concept that is built on Ni, Al, Ti, and Si (see FIG. 6 ) as hardening elements.
- a powder with chemical compositions according to FIG. 7 and a grain fraction of 15-45 ⁇ m is produced by means of gas atomization.
- bar stock which has been melted in the vacuum induction furnace and possibly remelted by means of ESR electroslag remelting) or VAR (vacuum arc remelting) is melted with the identical composition in a vacuum induction furnace and then atomized by means of inert gas (Ar, He, N).
- the powder fraction is adjusted by means of subsequent straining.
- the resulting powder fraction is then processed to produce sample bodies in a 3D printer, which functions according to the principle of selective laser melting.
- the printed material is then characterized in different heat treatment states with regard to its structure, hardening/aging behavior, and mechanical properties.
- the state “as printed+aged” is compared to the state “printed+solution annealed+aged.”
- the solution annealing was carried out at 1000° C. for 1 h and the aging was carried out 3 h at 525° C.
- the hardness was then determined using the Rockwell method.
- the mechanical properties were determined by means of tensile testing.
- FIGS. 6 and 7 show the characteristic values of a plurality of alloys with regard to hardness and toughness.
- the alloys V21, V311, V321, and V322 according to Table 1 correspond to the alloys according to the invention.
- FIG. 6 shows that the corresponding alloys according to the invention lie in the upper range of hardness of all of the alloys and thus have absolutely sufficient hardness properties.
- FIG. 7 shows the percentage of austenite as a function of the aging temperature.
- different percentages of retransformed austenite were produced, the retransformed austenite being responsible for the toughness of the material.
- the alloys according to the invention are all very close to one another, particularly with an aging temperature of 525° C., and the percentages of austenite are absolutely sufficient for the high level of toughness.
- the invention enables a particularly successful combination of hardness and toughness.
- the hardness after the aging is greater than 50 HRC.
- the results of the mechanical testing turn out differently between “printed+aged” and “printed+solution annealed+aged.”
- the printed and aged material that is not according to the invention has mechanical properties that lag those of conventionally heat-treated, solution annealed, and aged material.
- Table 3 shows the tensile strength and hardness values for printed, heat treated materials that are not according to the invention.
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DE102017131218.8A DE102017131218A1 (de) | 2017-12-22 | 2017-12-22 | Verfahren zum Herstellen eines Gegenstands aus einem Maraging-Stahl |
DE102017131218.8 | 2017-12-22 | ||
PCT/EP2018/085788 WO2019121879A1 (de) | 2017-12-22 | 2018-12-19 | Verfahren zum additiven fertigen eines gegenstandes aus einem maraging-stahlpulver |
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US (1) | US20230392243A2 (de) |
EP (1) | EP3728675B1 (de) |
JP (1) | JP7123143B2 (de) |
CN (1) | CN111670262A (de) |
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JP6985940B2 (ja) * | 2018-01-09 | 2021-12-22 | 山陽特殊製鋼株式会社 | 造形用のステンレス鋼粉末 |
US20230104535A1 (en) * | 2019-12-20 | 2023-04-06 | Arcelormittal | Process for the additive manufacturing of maraging steels |
WO2022200170A1 (en) * | 2021-03-22 | 2022-09-29 | Basf Se | Mim feedstock and process for manufacturing of metal parts with improved yield strength and ductility |
EP4166259B1 (de) * | 2021-10-14 | 2024-04-24 | Sandvik Machining Solutions AB | Metallpulver für die generative fertigung |
CN114351048B (zh) * | 2021-12-20 | 2022-08-30 | 广东省科学院中乌焊接研究所 | 一种马氏体时效钢粉末及在增材制造中应用 |
CN114619047B (zh) * | 2022-02-21 | 2023-08-01 | 国营芜湖机械厂 | 一种开启机构橡胶活塞杆模具制造方法 |
CN115029646B (zh) * | 2022-05-23 | 2024-01-16 | 上海交通大学 | 一种增材制造的超高强不锈钢 |
CN115156555B (zh) * | 2022-09-08 | 2022-12-06 | 季华实验室 | 新型15-5ph不锈钢材料及其增材制造方法 |
CN115446331B (zh) * | 2022-09-21 | 2024-03-05 | 华北理工大学 | 一种纯金属过配粉体选区激光熔化制备高氮不锈钢的方法 |
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CS192406B1 (en) * | 1977-03-30 | 1979-08-31 | Josef Dusek | High-strength steel containing chromium,nickel and molybdenum |
JPS6036649A (ja) * | 1983-08-05 | 1985-02-25 | Nisshin Steel Co Ltd | 靭性に優れたマルテンサイト系析出硬化型ステンレス鋼 |
JPH02310339A (ja) * | 1989-05-24 | 1990-12-26 | Kawasaki Steel Corp | 強度、バネ特性及び成形性に優れたマルテンサイト系ステンレス鋼 |
SE466265B (sv) * | 1990-05-29 | 1992-01-20 | Uddeholm Tooling Ab | Utskiljningshaerdande verktygsstaal |
SE469986B (sv) | 1991-10-07 | 1993-10-18 | Sandvik Ab | Utskiljningshärdbart martensitiskt rostfritt stål |
US6238455B1 (en) | 1999-10-22 | 2001-05-29 | Crs Holdings, Inc. | High-strength, titanium-bearing, powder metallurgy stainless steel article with enhanced machinability |
DE60331111D1 (de) | 2002-11-19 | 2010-03-11 | Hitachi Metals Ltd | Verfahren zur Herstellung von martensitaushärtendem Stahl |
DE102007056259A1 (de) * | 2007-11-21 | 2009-06-04 | Cl Schutzrechtsverwaltungs Gmbh | Laserschmelz- oder Sinterverfahren zur Herstellung dreidimensionaler Werkstücke |
JP5409708B2 (ja) * | 2011-06-16 | 2014-02-05 | 株式会社日立製作所 | 析出硬化型マルテンサイト系ステンレス鋼と、それを用いた蒸気タービン長翼 |
JP5764503B2 (ja) * | 2012-01-19 | 2015-08-19 | 三菱日立パワーシステムズ株式会社 | 析出硬化型マルテンサイト系ステンレス鋼、それを用いた蒸気タービン長翼、タービンロータ及び蒸気タービン |
JP6317542B2 (ja) * | 2012-02-27 | 2018-04-25 | 三菱日立パワーシステムズ株式会社 | 蒸気タービンロータ |
JP6049331B2 (ja) * | 2012-07-03 | 2016-12-21 | 株式会社東芝 | 蒸気タービンの動翼、蒸気タービンの動翼の製造方法および蒸気タービン |
EP3109033A1 (de) * | 2015-06-25 | 2016-12-28 | Airbus Operations GmbH | Pressform, pressformwerkzeug und pressformverfahren |
US10316712B2 (en) * | 2015-12-18 | 2019-06-11 | Exxonmobil Research And Engineering Company | Lubricant compositions for surface finishing of materials |
SE539763C2 (en) | 2016-06-16 | 2017-11-21 | Uddeholms Ab | Steel suitable for plastic molding tools |
CN106825566A (zh) * | 2017-01-11 | 2017-06-13 | 华南理工大学 | 一种激光选区熔化成型马氏体时效钢模具的方法 |
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JP2021512999A (ja) | 2021-05-20 |
WO2019121879A1 (de) | 2019-06-27 |
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