EP2470682A1 - Soft magnetic ferritic chromium steel - Google Patents
Soft magnetic ferritic chromium steelInfo
- Publication number
- EP2470682A1 EP2470682A1 EP10771635A EP10771635A EP2470682A1 EP 2470682 A1 EP2470682 A1 EP 2470682A1 EP 10771635 A EP10771635 A EP 10771635A EP 10771635 A EP10771635 A EP 10771635A EP 2470682 A1 EP2470682 A1 EP 2470682A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- magnetic
- chromium
- nickel
- annealing
- steel
- 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.)
- Granted
Links
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 55
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 230000007797 corrosion Effects 0.000 claims abstract description 27
- 238000005260 corrosion Methods 0.000 claims abstract description 27
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 23
- 239000011651 chromium Substances 0.000 claims abstract description 23
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 22
- 239000010941 cobalt Substances 0.000 claims abstract description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 20
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 19
- 239000010955 niobium Substances 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 239000011733 molybdenum Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011575 calcium Substances 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 238000000137 annealing Methods 0.000 claims description 41
- 229910000831 Steel Inorganic materials 0.000 claims description 38
- 239000010959 steel Substances 0.000 claims description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910000669 Chrome steel Inorganic materials 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 28
- 150000004763 sulfides Chemical class 0.000 description 25
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- 230000035699 permeability Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005482 strain hardening Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 230000005294 ferromagnetic effect Effects 0.000 description 6
- 229910052976 metal sulfide Inorganic materials 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 238000010671 solid-state reaction Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical class [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000005292 diamagnetic effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- VCTOKJRTAUILIH-UHFFFAOYSA-N manganese(2+);sulfide Chemical class [S-2].[Mn+2] VCTOKJRTAUILIH-UHFFFAOYSA-N 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 2
- -1 tungsten carbides Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010010219 Compulsions Diseases 0.000 description 1
- 229910000915 Free machining steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
-
- 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
- C22C38/42—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
- C22C38/44—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
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
-
- 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
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- 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
- C21D2211/005—Ferrite
Definitions
- Such steels are widely known and, depending on their particular composition, are suitable for a variety of uses depending on the composition.
- US Pat. No. 5,496,515 describes a ferritic stainless steel with improved machinability.
- This steel consists of at most 0.17% carbon, up to 2.0% silicon, up to 2.0% manganese, up to 0.55% sulfur, 11 to 20% chromium, up to 3.0% molybdenum, the highest 30 x 10 " 4% calcium, less than 1, 0% nickel and about 70 x 10 -4% oxygen with exudates from the phase diagram of CaO-SiO 2 -.
- U. S. Patent Specification 2007 01 66 183 describes a corrosion-resistant chromium ferritic steel with at most 0.025% carbon, at most 0.025% nitrogen, 1.0-0.2% silicon, at most 0.6% manganese, 0.15-0, 40% sulfur, 12-14% chromium, up to 0.5% copper, 0.5-1.3% molybdenum, 0.5-1.3% vanadium, up to 0.02% aluminum and up to 0.5% nickel , Remainder iron, whose corrosion resistance is impaired in view of the presence of manganese sulfides in the structure.
- German patent 10 2004 063 161 B4 0.15 to 0.65 in describes a moldable katlver- 'corrosion-resistant chromium steel containing 0.005 to 0.05% carbon, up to 0.01% nitrogen, 0.3 to 1, 0% of manganese, % Sulfur, 14 to 20% chromium, 0.2 to 1, 0% copper, 0.1 to 1, 0% molybdenum, 0.005 to 0.08% niobium, vanadium and titanium, up to 0.8% nickel, and singly or 0.01 to 0.1% lead, 0.01 to 0.5% bismuth, 0.01 to 0.1% arsenic, 0.01 to 0.1% antimony, 0.005 to 0.08% zirconium, and in each case up to 0.20% selenium and tellurium, the remainder iron including impurities caused by melting.
- soft magnetic ferritic steels must have a high reproducibility in terms of their coercive force. Accordingly, a deterioration of its coercive force caused by the cold working can be eliminated by annealing with the aim of reducing the work hardening again and thereby regaining the initial state before cold working as much as possible. However, this is only possible if the microstructure is thermodynamically sufficiently stable.
- ferritic chromium steels not only have to be sufficiently resistant to corrosion, but also have favorable soft-magnetic properties and must be easy to machine, in particular easy to machine.
- this is not achievable in many cases, which is related to the fact that the ferritic steels are very soft and therefore it comes during welding or deformation to welds and adhesions on the material.
- adhesions or weldings cause a low tool life associated with a defective surface quality, in particular smoothness.
- the reason for this is that the adhesions and welds resulting from cold welding under the influence of the cutting pressure are torn off.
- the practice requires as far as possible burr-free holes, grooves or blind holes.
- the problem of the soft magnetic ferritic chromium steels is therefore still to achieve a good machinability in conjunction with a low coercive force and sufficient corrosion resistance.
- the precipitates reduce the occurrence of cold welds during machining, they increase the tool life.
- some precipitates are magnetically nearly impermeable. The consequence of this is an increase in coercive force.
- the magnetic flux or magnetic flux lines characterizing it bypass the precipitates mentioned, requiring higher magnetic field strengths and energies with respect to a given magnetic flux, as reflected in increased coercive force.
- the electrochemical corrosion potential of the precipitates is greatly different and therefore forms areas of increased corrosion resistance. Although this could be counteracted by an increase in the chromium content, however, the chromium is non-magnetic and thus deteriorates the ferromagnetic properties of the steel.
- Fig. 1 of the drawing shows schematically.
- 1 denotes the ferritic matrix, 2 magnetic field lines, 3 magnetically permeable precipitates, 4 magnetically hardly permeable precipitates and 4 the grain boundaries.
- the problem underlying the invention is to provide a soft magnetic ferritic steel, which is characterized by good machinability with low tendency to burr formation during machining, high corrosion resistance and in particular good reproducibility of its properties.
- the solution to this problem is a specific composition of the steel with certain sulphide precipitates and, on the other hand, prevents the formation of harmful precipitates.
- the solution to the problem is a soft magnetic ferritic chrome steel with up to 0.025% carbon
- the steel preferably contains
- the aluminum is a very strong oxidizing agent and combines with the oxygen of the melt to very stable Tonerdeausscheidungen that increase the magnetic coercive force in magnetic steels due to their low magnetic permeability and susceptibility or their diamagnetism.
- the steel therefore contains at most 0.025%, preferably at most 0.020% aluminum.
- the carbon is not undesirable, but it increases the strength and hardenability. In addition, it forms with the elements chromium, titanium, vanadium, niobium and tungsten carbides, which reduce both the corrosion resistance and the coercive force increase adversely. In addition, since carbon promotes the formation of austenite, the steel should contain as little carbon as possible and the carbon content should not exceed 0.025%.
- Nitrogen forms hard precipitates with aluminum, chromium, titanium, vanadium and niobium, magnetically unfavorable in soft magnetic steels and also has an austenite-stabilizing effect.
- the nitrogen content is therefore not more than 0.02%.
- Chromium as a carbide former, increases wear resistance and provides at least a 12% level of corrosion resistance, although chromium, at over 18.0% as a diamagnetic alloying element, reduces magnetization in the ferrite.
- the chromium content is therefore 12.0 to 18.0%.
- the molybdenum reduces the critical cooling rate and forms stable carbides with the carbon. In combination with the chromium, it improves the corrosion resistance, but also increases the magnetic resistance as a diamagnetic element.
- the molybdenum content is therefore 0.5 to 3.0%.
- the vanadium is a strong carbide, nitride and sulfide former; It occurs in several oxidation stages and also forms mixed sulphides with high magnetic permeability (susceptibility), in particular as a consequence of reactions with the ferromagnetic nickel and cobalt. Furthermore, vanadium sulfides are advantageous for good chip breaking. The vanadium also forms important nuclei together with the niobium. A vanadium content of 0.4 to 1.2% therefore ensures both favorable magnetic properties and high corrosion resistance. Preferably, the vanadium content is at least 0.5%.
- the titanium is a strong deoxidizer and forms stable oxides, carbides, nitrides and sulfides, but with unfavorable magnetic properties.
- the titanium content is therefore only 0.06% at the most.
- the niobium is also one of the strong carbide, nitride and sulfide formers; It also stabilizes the ferrite and, as sulfide formers, forms primary nuclei that act as centers of crystallization.
- the niobium content is therefore 0.002 to 0.35%.
- the manganese forms sulfides with vacancies which have a very high magnetic permeability (susceptibility). With ferromagnetic metals such as nickel and cobalt, manganese also forms mixed sulfides. In addition, the manganese sulfide, in particular stabilized manganese sulfide improves the chip breaking behavior. On the other hand, manganese also stabilizes austenite. The manganese content is therefore 0.30 to 1, 5%, preferably at most 0.7%. The sulfur at 0.20 to 0.35% forms sulfides, with the help of which the machinability is improved. These sulfides act as breaker nuclei and therefore improve the separation of the chips. However, since sulfur also forms substoichiometric sulfides and mixed sulfides with vanadium, manganese, cobalt and nickel, thermal post-treatment is recommended for improving magnetic properties and corrosion resistance.
- nickel and cobalt belong to the ferromagnetic metals, but in chromium steels they expand the austenitic gamma region at the expense of ferrite. Since both elements form with the sulfur magnetically stable sulfides with high magnetic susceptibility, the nickel content is 0.01 to 1.0% and the cobalt content 0.01 to 0.4%.
- the annealing temperature is preferably at most 380 C C.
- the steel according to the invention is also characterized by a low coercive force and is therefore suitable, for example, for the production of solenoid valves, which should have the lowest possible residual magnetism when switching off the current to supply a coil to avoid permanent magnetic force effects and the associated reduction in switching speed ,
- the steel according to the invention is further characterized by a high corrosion resistance, which ensures a maintenance of the surface condition and is just in functional components of great importance to keep the coefficient of friction and the surface roughness and smoothness constant for the longest possible use.
- Functional components are to be understood here as meaning metallic components which are used under the action of forces and accelerations, for example components of a device for injecting fuel into an engine or like the parts of a solenoid valve. Functional components are generally subject to heavy wear, corrosion and magnetic forces.
- the invention is based on three mechanisms of action.
- the invention aims to avoid alloy components and precipitates with a high magnetic resistance, which displace the magnetic flux or flux lines.
- the chromium steel is therefore composed so that it contains primarily only such precipitates, which have a good magnetic permeability, ie are paramagnetic.
- the invention avoids precipitates having a high magnetic resistance or poor magnetic permeability.
- the analysis avoids precipitates having a high magnetic resistance or poor magnetic permeability.
- the second mechanism of action results from the fact that the micro-machinability is reduced by thermally modified sulfide-promoting, in particular burr-reducing sulfides.
- the third mechanism of action results from the fact that the corrosion sensitivity of sulfur-containing precipitates is reduced by a thermodynamic stabilization and interaction with certain elements in the matrix by means of a solid-state reaction.
- annealing preferably pendulum annealing
- pendulum annealing can be at a higher temperature stoichiometric, so not the actual proportions in the material corresponding and defects containing precipitates in the way of Transform solid-state reactions into more stable precipitates that no longer react with elements of the steel matrix and therefore retain their specific properties as in the present case, the magnetic permeability.
- a certain temperature range is required because at high temperatures certain elements remain dissolved in the steel matrix, while at too low temperatures, the diffusion and exchange reactions take place too slowly. Accordingly, the range of the annealing temperature is of crucial importance.
- the embedded in the basic structure sulfides can be modified accordingly in the pendulum annealing advantageous.
- a pendulum annealing with for example 1 to 3 cycles can take place below 400 0 C as the results from the graph of Fig. 2 for a duration of from 30 to 160 minutes at 600 to 900 0 C and a at least 30 minute final annealing at temperatures. Between two cycles in each case the temperature is reduced to under, ie here, for example, below 600 0 C, as shown in Fig. 2 is illustrated.
- the pendulum annealing In pendulum annealing, the sulfide precipitates stabilize, which subsequently show less solubility in contact with corrosive media and water resulting in better corrosion resistance. Surprisingly, the pendulum annealing also has an effect on improving the magnetic properties. This may be attributed to the fact that the ferromagnetic elements in the order of nickel, cobalt have an increasing affinity for sulfur and therefore can be effectively incorporated into the sulfide precipitates in pendulum annealing also in this order.
- Me may mean, for example, vanadium, niobium or manganese, while in the reaction equations 3 and 4, the cobalt may also be replaced by nickel.
- Manganese sulphides can also form mixed sulphides despite the high density of vacancies. Accordingly, MeCo and MeNi mixed sulfides of manganese and vanadium, whose nickel and / or cobalt content originate from the basic structure, can form from the resulting sulfides. This may be the reason why the susceptibility as a measure of the magnetic permeability (permeability) of Manganese and vanadium sulfide due to the incorporation of ferromagnetic net cobalt and nickel advantageously increased in these sulfides.
- the cobalt sulfide or mixed sulfide formed by the reaction equations 1 or 3 has a higher magnetic susceptibility than the nickel sulfide of Equation 2, it shows why the effect of the cobalt is better than that of the nickel, although both effects are advantageous.
- the expensive cobalt seems to have a stronger effect than the nickel, which also reacts with sulfur.
- the nickel content should not exceed 1% and the cobalt content should not exceed 0.5%.
- the improvement in corrosion resistance achievable with pendulum annealing can be explained by the fact that the sulfides formed during annealing are more thermodynamically stable and thus less soluble.
- This stabilization of the sulphide precipitates has a positive effect insofar as further annealing treatments, for example after cold forming and at higher temperatures, for example at 800 ° C., hardly influence the coercive force which, as in experiment 8, returns to about the original value.
- This is advantageous in that it is associated with a higher manufacturing reliability and reproducibility of the material properties.
- the steel according to the invention has a low coercive force, which is maintained even under the influence of higher temperatures, because the magnetizable precipitates are thermodynamically stable or stabilized by the annealing according to the invention, in particular pendulum annealing.
- This annealing serves the purpose of preventing further reactions of precipitates. This ultimately results in a high constancy of the magnetic properties.
- Samples 1 to 4 are samples according to the invention, while samples V 1 and V 4 concern comparison samples.
- Table 2 shows the coercive force of the test steels as a function of the number of annealing treatments and the pendulum annealing.
- the tests 1 to 4 and 11 to 18 relate to a conventional case of ferritic chromium steels annealing treatment at 800 0 C, while the Experiments 5 to 10, a pendulum were subjected to annealing in the temperature-time-critical range. While in the comparison steels 11 to 18, the coercive force HC is higher and therefore less favorable than in the inventive steels of Experiments 5 to 10, these have uniformly low coercive force in each case two pendulum anneals.
- Table 4 shows the results of a modified salt spray test.
- the samples covered by the invention and the comparative samples were sprayed for 120 hours in a test chamber with a 3% NaCl solution in a first series of experiments.
- the 3% NaCl solution additionally contained 3% sodium sulfite (Na 2 SO 3 ) and 3% ammonia. chloride (NH 4 Cl) and 5% methanol.
- This series of tests is marked “Z" in Table 4.
- the table also indicates in hours the period of time which elapsed until the first spots of rust or rust appeared, and if not, the samples were indicated by the indication "none" ,
- the samples were evaluated as 1 to 5 in terms of the frequency and / or amount of rusting spots.
- 1 stands for "no rust”
- 2 for two to three rust spots
- 3 for three to four rust spots
- 4 for four to five rust spots
- 5 for "rust spots larger than 2 mm 2 ".
- the samples were also subjected to micro-drilling tests with fine carbide micro-drills of diameter Db 0.5 mm and a speed of 35,000 rpm.
- the hole depth was uniformly 4.0 mm in all experiments.
- the tendency to burr formation was derived from two values in each case, namely by the burr width GB and the burr height H.
- the burr width was calculated according to the
- ferritic manganese steels Since cold working always increases the coercive force, ferritic manganese steels must always be subjected to annealing after cold working to reduce the increased coercive force in order to reduce the increase in coercive force and, if possible, to return to their initial value.
- the pendulum annealing is therefore directed to stabilize the partially unstable sulfides and thus their magnetic permeability. Accordingly, it is essential that the sulfides are thermodynamically stabilized and do not change in an annealing, such as a stress relief annealing.
- the steel according to the invention is characterized by a high manufacturing reliability or reproducibility, as evidenced by the results of tests 5, 6, 7 and 8.
- These experimental results show that thermodynamically stabilizing the sulfide precipitates by means of pendulum annealing in the steel according to the invention is also advantageous in micro-machining by means of lower GB values and in particular leads to a lower burr formation. Added to this is the better corrosion resistance of the steels, as illustrated by the results of tests 5 to 10 in comparison to the experiments 11 to 18.
- nn not detectable
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DE200910038386 DE102009038386A1 (en) | 2009-08-24 | 2009-08-24 | Soft magnetic ferritic chrome steel |
PCT/EP2010/005150 WO2011023349A1 (en) | 2009-08-24 | 2010-08-23 | Soft magnetic ferritic chromium steel |
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DE102014202570A1 (en) * | 2014-02-12 | 2015-08-13 | BSH Hausgeräte GmbH | Electric drive motor, pump and household appliance with such a pump |
WO2018105698A1 (en) * | 2016-12-08 | 2018-06-14 | 新日鐵住金株式会社 | Steel material for soft magnetic component, soft magnetic component, and method for manufacturing soft magnetic component |
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DE1783136C2 (en) * | 1965-10-22 | 1975-10-02 | Stahlwerke Suedwestfalen Ag, 5930 Huettental-Geisweid | Use of an easily machinable, rustproof, magnetically soft chromium steel for solenoid valves |
US3615367A (en) * | 1968-07-31 | 1971-10-26 | Armco Steel Corp | Low-loss magnetic core of ferritic structure containing chromium |
FR2720410B1 (en) | 1994-05-31 | 1996-06-28 | Ugine Savoie Sa | Ferritic stainless steel with improved machinability. |
WO1996011483A1 (en) | 1994-10-11 | 1996-04-18 | Crs Holdings, Inc. | Corrosion-resistant magnetic material |
US5769974A (en) * | 1997-02-03 | 1998-06-23 | Crs Holdings, Inc. | Process for improving magnetic performance in a free-machining ferritic stainless steel |
DE10143390B4 (en) * | 2001-09-04 | 2014-12-24 | Stahlwerk Ergste Westig Gmbh | Cold-formed corrosion-resistant chrome steel |
FR2832734B1 (en) * | 2001-11-26 | 2004-10-08 | Usinor | SULFUR FERRITIC STAINLESS STEEL, USEFUL FOR FERROMAGNETIC PARTS |
DE102004063161B4 (en) | 2004-04-01 | 2006-02-02 | Stahlwerk Ergste Westig Gmbh | Cold forming chromium steel |
US20070166183A1 (en) | 2006-01-18 | 2007-07-19 | Crs Holdings Inc. | Corrosion-Resistant, Free-Machining, Magnetic Stainless Steel |
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