EP3914738A1 - Iron-manganese alloy having improved weldability - Google Patents
Iron-manganese alloy having improved weldabilityInfo
- Publication number
- EP3914738A1 EP3914738A1 EP19702970.5A EP19702970A EP3914738A1 EP 3914738 A1 EP3914738 A1 EP 3914738A1 EP 19702970 A EP19702970 A EP 19702970A EP 3914738 A1 EP3914738 A1 EP 3914738A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alloy
- weight
- iron
- invar
- hot
- 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.)
- Pending
Links
- 229910000914 Mn alloy Inorganic materials 0.000 title claims abstract description 24
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000011572 manganese Substances 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 82
- 239000000956 alloy Substances 0.000 claims description 82
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000011651 chromium Substances 0.000 claims description 17
- 239000011265 semifinished product Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 11
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 10
- 230000009466 transformation Effects 0.000 claims description 10
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 6
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001374 Invar Inorganic materials 0.000 description 50
- 238000012360 testing method Methods 0.000 description 38
- 238000005260 corrosion Methods 0.000 description 22
- 230000007797 corrosion Effects 0.000 description 22
- 238000005336 cracking Methods 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 9
- 239000011669 selenium Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 238000005098 hot rolling Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010964 304L stainless steel Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 230000000712 assembly Effects 0.000 description 3
- 238000000429 assembly Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 229910002551 Fe-Mn Inorganic materials 0.000 description 2
- 229910001122 Mischmetal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910000617 Mangalloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000002885 antiferromagnetic material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052745 lead 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- 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
- C21D6/004—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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
-
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
-
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
-
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
-
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
- C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
-
- 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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
-
- 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
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
-
- 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
-
- 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
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
-
- 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
Definitions
- the present invention relates to an iron-manganese alloy for use in making parts and welds for applications where high dimensional stability under the effect of temperature variations is required, particularly at cryogenic temperatures.
- the alloy according to the invention is more particularly intended for use in the field of electronics, as well as in cryogenic applications.
- the alloys most commonly used for such applications are iron-nickel alloys, and more particularly Invars®, generally comprising about 36% nickel.
- Such alloys exhibit excellent dimensional stability properties, in particular at cryogenic temperature, but have the drawback of a relatively high production cost resulting in particular from their relatively high nickel content.
- the weldability of these alloys on other metals is not always entirely satisfactory, especially in terms of the mechanical strength of heterogeneous welds.
- iron-based alloys also comprising carbon and manganese sold by the Korean company Posco. These steels include, by weight:
- one aim of the invention is to provide an alloy capable of being used satisfactorily for manufacturing parts and welded assemblies for applications in which high dimensional stability under the effect of temperature variations is required, for example for cryogenic applications, while having a relatively low cost price.
- the invention relates to an iron-manganese alloy comprising, by weight: 25.0% £ Mn £ 32.0%
- the alloy according to the invention comprises one or more of the following characteristics, taken in isolation or in any technically possible combination (s):
- the chromium content is between 8.5% and 11.5% by weight.
- the nickel content is between 0.5% and 2.5% by weight.
- Rare earths include one or more elements chosen from: lanthanum, cerium, yttrium, praseodymium, neodymium, samarium and ytterbium.
- the iron-manganese alloy as described above has an average coefficient of thermal expansion CTE between -180 ° C and 0 ° C less than or equal to 8.5.10 -6 / ° C.
- the iron-manganese alloy as described above has a Néel T Néel temperature greater than or equal to 40 ° C.
- the iron-manganese alloy as described above presents, when it is produced in a thin strip with a thickness less than or equal to 3 mm, at least one of the following characteristics:
- the iron-manganese alloy as described above is austenitic at cryogenic temperature and at room temperature.
- the invention also relates to a method of manufacturing a strip made of an alloy as defined above, the method comprising the following successive steps:
- This semi-finished product is hot-rolled in order to obtain a hot strip
- the hot strip is cold rolled in one or more passes to obtain a cold strip.
- the invention also relates to a strip made from an iron-manganese alloy as defined above.
- the invention also relates to a process for manufacturing a wire made from an iron-manganese alloy as defined above, the process comprising the following steps:
- the invention also relates to a wire made from an iron-manganese alloy as defined above.
- This wire is in particular a material supply wire or a wire intended for the manufacture of bolts or screws, these bolts and screws being obtained in particular by cold heading from this wire.
- the alloy according to the invention is an iron-manganese alloy comprising, by weight: 25.0% £ Mn £ 32.0%
- One such alloy is a high manganese austenitic steel.
- the alloy according to the invention is austenitic at room temperature and at cryogenic temperature (-196 ° C).
- residual elements resulting from the production we mean elements which are present in the raw materials used to develop the alloy or which come from the devices used for its production, and for example refractories in furnaces. These residual elements have no metallurgical effect on the alloy.
- the residual elements include in particular one or more elements chosen from: carbon (C), aluminum (Al), selenium (Se), sulfur (S), phosphorus (P), oxygen (O), cobalt (Co), copper (Cu), molybdenum (Mo), tin (Sn), niobium (Nb), vanadium (V), titanium (Ti) and lead (Pb).
- the maximum contents are preferably chosen as follows, by weight:
- Se £ 0.02% by weight and preferably Se £ 0.01% by weight, still more preferably Se £ 0.005% by weight,
- the selenium content is limited according to the ranges mentioned above in order to avoid hot cracking problems which could result from too high selenium presence in the alloy.
- the alloy according to the invention has in particular:
- this alloy has properties of thermal expansion, of resilience and of mechanical strength which are satisfactory for its use for the applications mentioned above, in particular at cryogenic temperature.
- the alloy according to the invention also exhibits corrosion resistance characterized by a critical corrosion current in an H 2 SO 4 medium (2 mol.l -1 ) strictly less than 230 mA / cm 2 and a pitting potential V in NaCl medium (0.02 mol.l -1 ) strictly greater than 40 mV, the pitting potential being determined by reference to a reference potential, the hydrogen electrode (ENH).
- the alloy according to the invention thus exhibits corrosion resistance greater than or equal to that of Invar®-M93.
- Invar®-M93 is a material usually used in the context of the applications mentioned above, in particular at cryogenic temperature.
- the alloy according to the invention also exhibits a corrosion resistance much greater than that observed for the earlier Fe-Mn alloys, which exhibit a critical corrosion current in an H 2 SO 4 medium (2 mol.l -1 ) greater than approximately 350mA / cm 2 and a pitting potential V less than or equal to -200 mV with respect to the hydrogen electrode (ENH).
- the alloy according to the invention also exhibits satisfactory weldability, and in particular good resistance to hot cracking. In particular, as explained below, it has a crack length less than or equal to 7 mm during a Varestraint test for 3% plastic deformation. Consequently, the alloy according to the invention exhibits a resistance to cracking much higher than that observed for the previous Fe-Mn alloys.
- manganese at a content less than or equal to 32.0% by weight, makes it possible to obtain an average coefficient of thermal expansion of less than 8.5.10 -6 / ° C between -180 ° C and 0 ° C.
- This thermal expansion coefficient is satisfactory for the use of the alloy in the context of the applications envisaged, and in particular in the context of cryogenic applications.
- the manganese content greater than or equal to 25.0% by weight combined with a chromium content less than or equal to 14.0% by weight, makes it possible to obtain good dimensional stability of the alloy at room temperature and at cryogenic temperature (-196 ° C).
- the Néel temperature of the alloy is then strictly greater than 40 ° C., and does not risk being reached at the usual temperatures of use of the alloy.
- using the alloy at temperatures above Néel's temperature risks generating significant variations in expansion of welded parts and assemblies at room temperature.
- the coefficient of expansion of the high manganese steel described above is of the order of 8.10 -6 / ° C at temperatures less than or equal to the Néel temperature, while it is order of 16.10 -6 / ° C for temperatures above Néel temperature.
- Chromium at a content of less than or equal to 14.0% by weight, makes it possible to obtain good KCV resilience on a reduced test piece of 3 mm thickness and at cryogenic temperature (-196 ° C), and in particular a KCV resilience at -196 ° C greater than or equal to 50 J / cm2. On the contrary, the inventors have observed that a chromium content of strictly greater than 14.0% by weight may result in too great a brittleness of the alloy at cryogenic temperature.
- chromium makes it possible to obtain good weldability of the alloy.
- the inventors have observed that the weldability tends to deteriorate for chromium contents strictly less than 7.0% by weight. Chromium also helps improve the corrosion resistance of the alloy.
- the chromium content is between 8.5% and 11.5% by weight.
- a chromium content within this range results in an even better compromise between a high Néel temperature and high corrosion resistance.
- Nickel at a content of less than or equal to 2.5% by weight, makes it possible to obtain an average coefficient of thermal expansion between -180 ° C and 0 ° C less than or equal to 8.5.10-6 ° / C. This coefficient of thermal expansion is satisfactory for the use of the alloy in the context of the applications envisaged. On the contrary, the inventors have observed that the coefficient of thermal expansion risks deteriorating for nickel contents strictly greater than 2.5% by weight.
- the nickel content is between 0.5% and 2.5% by weight.
- a nickel content greater than or equal to 0.5% by weight makes it possible to further improve the resilience of the alloy at cryogenic temperature (-196 ° C).
- Nitrogen at levels greater than or equal to 0.05% by weight, helps to improve corrosion resistance. However, its content is limited to 0.30% by weight in order to maintain satisfactory weldability and resilience at cryogenic temperature (-196 ° C.).
- the nitrogen content is between 0.15% and 0.25% by weight.
- a nitrogen content within this range makes it possible to obtain an even better compromise between mechanical properties and corrosion resistance.
- the silicon present in the alloy at a content of between 0.1% and 0.5% by weight, acts as a deoxidizer in the alloy.
- the alloy optionally comprises rare earths in a content of between 0.010% and 0.14% by weight.
- the rare earths are preferably chosen from yttrium (Y), cerium (Ce), lantan (La), praseodymium (Pr), neodymium (Nd), samarium (Sm) and ytterbium (Yb) or mixtures of one or more of these elements.
- the rare earths comprise a mixture of cerium and lanthanum or yttrium, used alone or mixed with cerium and lanthanum.
- the rare earths consist of lanthanum and / or yttrium, the sum of the lanthanum and yttrium contents being between 0.010% and 0.14% by weight.
- the rare earths consist of cerium, the cerium content being between 0.010% and 0.14% by weight.
- the rare earths consist of a mixture of lanthanum, yttrium, neodymium and praseodymium, the sum of the lanthanum, yttrium, neodymium and praseodymium contents being between 0.010% and 0.14% by weight.
- the rare earths are added, for example in the form of Mischmetal, in a content of between 0.010% and 0.14% by weight.
- Mischmetal contains lanthanum, yttrium, neodymium and praseodymium in the following proportions: Ce: 50%, La: 25%, Nd: 20% and Pr: 5%.
- rare earths and more particularly of a mixture of cerium and lanthanum or yttrium, at the contents mentioned above makes it possible to obtain an alloy exhibiting very good resistance to hot cracking, and consequently , further improved weldability.
- the rare earth content is between 150 ppm and 800 ppm.
- the alloy according to the invention can be produced by any suitable method known to those skilled in the art.
- the alloy according to the invention is produced in a vacuum oven from raw materials with low residuals.
- hot or cold strips are produced from the alloy thus produced.
- the alloy is cast in the form of semi-finished products such as ingots, reflow electrodes, slabs, in particular thin slabs with a thickness of less than 200 mm, in particular obtained by continuous casting, or billets.
- the alloy When the alloy is cast in the form of a reflow electrode, it is advantageously remelted under vacuum or in an electrically conductive slag in order to obtain better purity and more homogeneous semi-products.
- the semi-finished product thus obtained is then hot rolled at a temperature of between 950 ° C. and 1220 ° C. to obtain a hot strip.
- the thickness of the hot strip is in particular between 2 mm and 6.5 mm.
- the hot rolling is preceded by a heat treatment of chemical homogenization at a temperature between 950 ° C and 1220 ° C for a period of between 30 minutes to 24 hours.
- the chemical homogenization process is carried out in particular on the slab, in particular the thin slab.
- the hot strip is cooled to room temperature to form a cooled strip and then wound into coils.
- the cooled strip is then cold rolled to obtain a cold strip having a final thickness advantageously between 0.5 mm and 2 mm.
- Cold rolling is carried out in one pass or in several successive passes.
- the cold strip is, optionally, subjected to a recrystallization heat treatment in a static oven for a period ranging from 10 minutes to several hours and at a temperature above 700 ° C.
- a recrystallization heat treatment in a continuous annealing furnace for a period ranging from a few seconds to approximately 1 minute, at a temperature above 900 ° C. in the holding zone of the furnace, and in a protected atmosphere.
- N2 / H2 type (30% / 70%) with a frost temperature between -50 ° C and -15 ° C.
- the frost temperature defines the partial pressure of water vapor contained in the heat treatment atmosphere.
- a recrystallization heat treatment can be carried out, under the same conditions, during cold rolling, at an intermediate thickness between the initial thickness (corresponding to the thickness of the hot strip) and the final thickness.
- the intermediate thickness is for example chosen equal to 1.5 mm when the final thickness of the cold strip is 0.7 mm.
- the method for developing the alloy and for manufacturing hot and cold strips of this alloy are given only by way of example. All other methods for producing the alloy according to the invention and for manufacturing finished products made from this alloy known to those skilled in the art can be used for this purpose.
- the invention also relates to a strip, and in particular a hot or cold strip, made from the alloy as described above.
- the strip has a thickness less than or equal to 6.5 mm, and preferably less than or equal to 3 mm.
- Such a strip is, for example, a cold strip produced by the process described above or a hot strip obtained at the end of the hot rolling step of the process described above.
- the invention also relates to a wire made from the alloy described above.
- the wire is a material filler wire intended to be used to weld parts together.
- the wire intended is for the manufacture of bolts or screws, these bolts and screws being obtained in particular by cold heading from this wire.
- such a wire is manufactured by implementing a process comprising the following steps:
- the semi-finished product is in particular an ingot or a billet.
- These semi-finished products are preferably transformed by hot processing between 1050 ° C and 1220 ° C to form the intermediate yarn.
- the semi-products that is to say in particular the ingots or billets
- the semi-products are hot transformed so as to reduce their section, by giving them, for example, a square section, about 100mm to 200mm square.
- the length of this semi-finished product of reduced section is in particular between 10 meters and 20 meters.
- the reduction of the section of the semi-finished products is carried out by one or more successive hot rolling passes.
- the semi-finished products of reduced cross-section are then again hot-processed to obtain the wire.
- the wire can in particular be a machine wire. It has for example a diameter of between 5mm and 21mm, and in particular approximately equal to 5.5mm.
- the wire is produced by hot rolling on a wire train. Testing
- the inventors have produced laboratory castings of alloys exhibiting compositions as defined above, as well as of comparative alloys exhibiting compositions different from the composition described above.
- the inventors carried out Varestraint tests on the strips obtained according to the European standard FD CEN ISO / TR 17641-3 under 3.2% plastic deformation in order to assess their resistance to hot cracking. They measured the total length of cracks developed during the test, and classified the bands into three categories:
- Hot cracking resistance is an important aspect of the weldability of an alloy, the weldability being all the better as the cracking resistance is important.
- the inventors also tested the corrosion resistance by carrying out potentiometric tests. To this end, they carried out the following tests:
- Invar®-M93 has the following composition, in percentage by weight:
- Invar corresponds to bands for which J steel Mn ⁇ J Invar M93 and V steel Mn / E ENH > V Invar M93 / E ENH ;
- ⁇ Invar corresponds to bands for which J steel Mn > J Invar M93 or V steel Mn / E ENH ⁇ V Invar M93 / E ENH ;
- ⁇ Invar corresponds to bands for which J steel Mn ⁇ J Invar M93 or V steel Mn / E ENH ⁇ V Invar M93 / E ENH .
- the inventors also carried out impact tests at -196 ° C on a reduced specimen (thickness ⁇ 3.5mm) and measured the breaking energy by impact of the strip (denoted KCV), in accordance with standard NF EN ISO 148- 1.
- the fracture energy is expressed in J / cm2. It reflects the resilience of the band.
- the results of these tests are summarized in the column entitled “KCV at -196 ° C” of Table 1 below.
- the inventors also carried out dilatometric tests:
- Néel's temperature corresponds to the temperature above which an antiferromagnetic material becomes paramagnetic.
- the average coefficient of thermal expansion is determined by measuring the variation in length in micrometers between -180 ° C and 0 ° C of a 50 mm length test piece at 0 ° C. The average coefficient of thermal expansion is then obtained by applying the following formula: where L 0 - L 1 represents the
- L 0 represents the length of the test piece at 0 ° C
- T 0 is equal to 0 ° C
- T 1 is equal to -180 ° C.
- Néel's temperature is determined by measuring L (T), where L is the length of the sample at temperature T, and then calculating the slope dL / dT.
- the Néel temperature corresponds to the temperature of the change in slope of this curve.
- min means N ⁇ 0.03% by weight. At these levels, nitrogen is considered a residual element.
- mini means that the alloy comprises at most traces of these elements, preferably a content of each of these elements less than or equal to 1 ppm.
- these bands have a corrosion resistance greater than or equal to that of Invar M93, an average coefficient of thermal expansion CTE between - 180 ° C and 0 ° C less than or equal to 8.5.10 -6 / ° C , a Néel temperature greater than or equal to 40 ° C, a KCV impact strength at -196 ° C greater than or equal to 80 J / cm2 and a yield strength Rp 0.2 at -196 ° C greater than or equal to 700 MPa .
- the strips produced in the alloy according to the invention therefore exhibit properties of thermal expansion, of resilience and of mechanical resistance which are satisfactory for their use for applications for which high dimensional stability under the effect of temperature variations is required, in particular. at cryogenic temperature.
- the alloys according to the tests numbered 1 to 5 have a chromium content strictly less than 7.0% by weight. It is observed that the corresponding bands exhibit poor resistance to hot cracking, and therefore unsatisfactory weldability. Furthermore, tests 1 and 3 show that this poor resistance to hot cracking is not compensated for by the addition of carbon, even at relatively high contents.
- the alloy according to test 11 has a chromium content of strictly greater than 14.0% by weight. It is observed that the corresponding bands exhibit significant brittleness at cryogenic temperature, resulting in a KCV resilience strictly less than 50 J / cm2. It is also observed that this alloy has a Néel temperature strictly lower than 40 ° C.
- the alloy according to test numbered 13 has a nickel content strictly greater than 2.5% by weight. It is observed that the corresponding bands exhibit an average coefficient of thermal expansion CTE between -180 ° C and 0 ° C strictly greater than 8.5.10 -6 / ° C.
- the bands corresponding to tests 14, 17, 19 and 20 which comprise rare earths in proportions of between 0.010% and 0.14% by weight, exhibit excellent resistance to hot cracking, with lengths of cracks less than 2 mm.
- the bands corresponding to tests 18 and 21 have a rare earth content strictly greater than 0.14% by weight, and it is found that these bands have degraded weldability.
- homogeneous welds were carried out by butt-welding two coupons taken together in strips made of Invar® M93 and heterogeneous welds by butt-welding together a coupon taken from a strip made of Invar® M93 and a coupon taken from a strip made of 304L stainless steel.
- the tensile tests were performed at room temperature as is customary for welding qualification tests.
- the alloy according to the invention can be advantageously used in any application in which good dimensional stability, associated with good corrosion resistance and good weldability are desired, in particular in the cryogenic field or in the field of electronics. .
- the alloys according to the invention can be advantageously used for the manufacture of welded assemblies intended for applications in which high dimensional stability under the effect of temperature variations is required, in particular at cryogenic temperature.
Abstract
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US (1) | US20220162728A1 (en) |
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DE2351234A1 (en) * | 1973-10-12 | 1975-04-17 | Nippon Steel Corp | Austenitic weldable manganese-chromium-nickel steel - has low coefft. of thermal expansion and good notch impact toughness at very low temp. |
GB1438884A (en) * | 1974-09-30 | 1976-06-09 | Allegheny Ludlum Ind Inc | Corrosion resistant austenitic steel |
JPS5236513A (en) * | 1975-09-18 | 1977-03-19 | Daido Steel Co Ltd | Strong and tough steel used at extremely low temperature |
JPS60204864A (en) * | 1984-03-29 | 1985-10-16 | Sanyo Tokushu Seikou Kk | Nonmagnetic high-mn steel having superior toughness at ordinary and low temperatures |
EP0174418B1 (en) * | 1984-05-22 | 1990-05-23 | Westinghouse Electric Corporation | Austenitic alloys based on iron-manganese and iron-manganese-chromium |
JPS61143563A (en) * | 1984-12-17 | 1986-07-01 | Nippon Steel Corp | Rust resistant, tough and hard high-manganese steel for use at very low temperature |
JPH0619110B2 (en) * | 1986-05-19 | 1994-03-16 | 株式会社神戸製鋼所 | Method for producing high Mn austenitic stainless steel for cryogenic use |
JPS63259026A (en) * | 1987-04-16 | 1988-10-26 | Nippon Mining Co Ltd | Manufacture of nonmagnetic material |
JPH0211723A (en) * | 1988-06-28 | 1990-01-16 | Kanai Hiroyuki | Manufacture of micro shaft |
US5278881A (en) * | 1989-07-20 | 1994-01-11 | Hitachi, Ltd. | Fe-Cr-Mn Alloy |
JP3152473B2 (en) * | 1992-01-20 | 2001-04-03 | 新日本製鐵株式会社 | Submerged arc welding method for high Mn non-magnetic steel |
WO1997003215A1 (en) * | 1995-07-11 | 1997-01-30 | Kari Martti Ullakko | Iron-based shape memory and vibration damping alloys containing nitrogen |
FR2796083B1 (en) * | 1999-07-07 | 2001-08-31 | Usinor | PROCESS FOR MANUFACTURING IRON-CARBON-MANGANESE ALLOY STRIPS, AND STRIPS THUS PRODUCED |
JP4529872B2 (en) * | 2005-11-04 | 2010-08-25 | 住友金属工業株式会社 | High Mn steel material and manufacturing method thereof |
CN101250674A (en) | 2008-04-11 | 2008-08-27 | 江苏大学 | Mid nitrogen high manganese austenitic stainless steel |
JP6078554B2 (en) * | 2011-12-27 | 2017-02-08 | ポスコPosco | Austenitic steel material excellent in cryogenic toughness in machinability and weld heat affected zone and method for producing the same |
KR20150066373A (en) | 2013-12-06 | 2015-06-16 | 주식회사 포스코 | Welded joint having excellent impact resistance and abrasion resistance properties |
KR101543916B1 (en) * | 2013-12-25 | 2015-08-11 | 주식회사 포스코 | Steels for low temperature services having superior deformed surface quality and method for production thereof |
SI2924131T1 (en) * | 2014-03-28 | 2019-12-31 | Outokumpu Oyj | Austenitic high-manganese stainless steel |
JP6693217B2 (en) * | 2015-04-02 | 2020-05-13 | 日本製鉄株式会社 | High Mn steel for cryogenic temperatures |
DE102017114262A1 (en) * | 2017-06-27 | 2018-12-27 | Salzgitter Flachstahl Gmbh | Steel alloy with improved corrosion resistance under high temperature stress and method of making steel strip from this steel alloy |
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