EP2695953B1 - Method for adding zinc to molten steel and process for producing zinc-containing steel - Google Patents
Method for adding zinc to molten steel and process for producing zinc-containing steel Download PDFInfo
- Publication number
- EP2695953B1 EP2695953B1 EP11862742.1A EP11862742A EP2695953B1 EP 2695953 B1 EP2695953 B1 EP 2695953B1 EP 11862742 A EP11862742 A EP 11862742A EP 2695953 B1 EP2695953 B1 EP 2695953B1
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- EP
- European Patent Office
- Prior art keywords
- zinc
- molten steel
- steel
- mass
- supplied
- Prior art date
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- 239000011701 zinc Substances 0.000 title claims description 148
- 229910000831 Steel Inorganic materials 0.000 title claims description 146
- 239000010959 steel Substances 0.000 title claims description 146
- 229910052725 zinc Inorganic materials 0.000 title claims description 143
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 122
- 238000000034 method Methods 0.000 title claims description 47
- 230000008569 process Effects 0.000 title claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- -1 zinc aluminate Chemical class 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 13
- 229910001315 Tool steel Inorganic materials 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 11
- 239000004110 Zinc silicate Substances 0.000 claims description 10
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 claims description 10
- 235000019352 zinc silicate Nutrition 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 52
- 150000003752 zinc compounds Chemical class 0.000 description 42
- 239000011787 zinc oxide Substances 0.000 description 26
- 239000000292 calcium oxide Substances 0.000 description 23
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 23
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 13
- 239000002893 slag Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 229910000851 Alloy steel Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 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
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- PGZIKUPSQINGKT-UHFFFAOYSA-N dialuminum;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O PGZIKUPSQINGKT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 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
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0006—Adding metallic additives
-
- 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
-
- 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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—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
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
Definitions
- the present invention relates to a method for adding zinc to a molten steel in a process of melting the steel, and to a process for producing a zinc-containing steel using the method.
- Zinc is a volatile element having a melting point and a boiling point much lower than those of a steel (iron). Therefore, when zinc is added in a form of a metal in a molten steel in a process of melting the steel, most of zinc evaporates and is lost from the steel immediately after its addition. Thus, yield percentage relative to an intended addition is poor. Therefore, a method of adding zinc to a steel has been proposed, in which zinc metal is previously coated with a material having the same composition as the molten steel with an insulating material such as paper or plastics therebetween, and the resultant is supplied to the molten steel, thereby preventing the decrease in the yield due to the zinc evaporation (see JP-2-61006 A ).
- RU 2 396 364 C1 discloses that as a flux a slag of aluminium production is used which contains: 1.0-60.0 wt% aluminium, 1.0-50.0 wt% aluminium oxide, 0.28-1.0 wt% calcium oxide, 1.0-10.0 wt% magnesium oxide, 1.0-9.0 wt% iron oxide, 1.0-16.0 wt% silicon oxide, 0.1-10.0 wt% copper oxide, 0.1-2.0 wt% manganese oxide, 0.2-12.0 wt% zinc oxide, 0.01-0.15 wt% lead oxide, 0.01-0.15 wt% nickel oxide, 0.05-0.5 wt% chromium oxide, 0.1-40.0 wt% sodium chlorides and 0.1-40.0 wt% potassium chlorides.
- JP-2-61006 A allows the zinc metal to penetrate deep into the molten steel and has an effect of improving the yield of zinc to a certain degree.
- a form of a zinc metal is added, still a large amount of zinc evaporates although some zinc melts into the molten steel. Further, a cost increase may be caused since the coating of the zinc metal needs a complex step. Therefore, a method that can further improve the yield of zinc in a simpler way is required.
- EP 1 669 471 A1 discloses a highly ductile steel sheet and a method of manufacturing the same. This document discloses a CaO slag containing CaO, Al 2 O 3 , SiO 2 , MgO, MnO and Fe. The document does not disclose zinc.
- EP 0 015 417 A1 describes a slag composition, which is merely a mixture of various oxides including ZnO. This mixture is not a composite oxide where zinc is combined with aluminum and/or silicon. It is not intended to add zinc to a molten steel during a process of melting the steel.
- An object of the present invention is to provide a method for adding zinc to a molten steel in a higher yield and in a simple way, and a process for producing a zinc-containing steel using the method.
- a main reason why added zinc evaporates immediately in the molten steel is because zinc is added in a form of a single metal.
- the present inventors have studied a method for adding zinc in a form of a compound. As a result, the present inventors have found that zinc aluminate and/or zinc silicate are suitable for achieving both a high yield of addition and a low cost, and have reached the present invention.
- a method for adding zinc to a molten steel including supplying zinc aluminate that is a composite oxide of ZnO and Al 2 O 3 and/or zinc silicate that is a composite oxide of ZnO and SiO 2 to the molten steel.
- the method may further comprise supplying an oxide of calcium to the molten steel.
- the molten steel is preferably used for the production of a hot work tool steel.
- the present invention also provides a process for producing a zinc-containing steel, including casting a molten steel added with zinc by the above method.
- the cast zinc-containing steel preferably includes not less than 0.001 mass% zinc.
- the present invention for example, not lower than 0.001 mass%, or as high as 0.01 mass% of zinc can be mixed in the steel with a good yield and at a low cost, and a steel including the above amount of zinc can be produced.
- the present invention is useful for producing a high zinc steel, such as the hot work tool steel as disclosed in Patent Literature 1.
- the compound supplied to the molten steel is a composite oxide of: zinc; and aluminum and/or silicon:
- a temperature of a molten steel reaches as high as 1600°C. Since a zinc metal has a low boiling point of about 900°C (and high vapor pressure), zinc rapidly evaporates after it is supplied to a molten steel and before the steel is casted. If the zinc metal is made into a zinc compound which is difficult to be decomposed (in other words, a vapor pressure of the zinc component is low) even at e.g. 1600°C in an open air environment and the zinc compound is supplied to a molten steel, the zinc component in the compound will not evaporate immediately and remains in the molten steel.
- the present inventors have studied on the zinc compounds which meet the above requirement. As a result, it has been found that a composite oxide of zinc and aluminum and a composite oxide of zinc and silicon are not easily decomposed at such a high temperature, while a simple oxide of zinc is more likely to be decomposed at a high temperature of 1600°C. These zinc compounds can be reduced by silicon, manganese, aluminum, magnesium or calcium that are usually present in a molten steel. Therefore, when the zinc component is added to a molten steel in the form of the composite oxide where zinc is combined with aluminum and/or silicon, the zinc component will not evaporate immediately and the reduction reaction is facilitated in the molten steel. As a result, more zinc metal is added to the molten steel.
- the zinc compound in the present invention may include zinc aluminate that is a composite oxide of ZnO and Al 2 O 3 , or zinc silicate that is a composite oxide of ZnO and SiO 2 .
- Zinc silicate has a lower melting point than zinc aluminate and is decomposed (or reduced) relatively faster. Therefore, a predetermined amount of zinc can be added to a molten steel in a short time. However, as the decomposition proceeds faster, zinc generated by the decomposition evaporates and escapes from the molten steel earlier than in the case of zinc aluminate. In an actual operation, a molten steel is usually cast less than one hour after a composition of the steel is adjusted.
- zinc silicate is supplied to the molten steel at the end of the adjustment of the composition, casting can be completed before a large amount of zinc escapes from the molten steel to which zinc silicate has been supplied.
- zinc silicate is suitable for the improvement of the yield of zinc.
- the reduction reaction of zinc aluminate progresses relatively slowly and therefore zinc aluminate can suppress strong fuming caused by the evaporation of zinc due to rapid decomposition of the zinc compound immediately after the supply to a molten steel.
- the use of zinc aluminate is preferred in that smoke extraction facility can be simplified in an actual operation.
- both of a composite oxide of zinc and aluminum and a composite oxide of zinc and silicon are used as the zinc compounds for supplying to the molten steel
- both of the composite oxides may be supplied to the molten steel, or alternatively a composite oxide in which zinc, aluminum and silicon are combined may be supplied.
- the zinc compound according to the present invention may be directly supplied to the molten steel, or it may be wrapped by e.g. a metal and inserted in the molten metal as far as properties of the steel are not affected.
- a surface of the molten steel is coated with the zinc compound.
- the zinc compound may also be inserted in a deep portion of the molten steel by using a charging guide or the like.
- an upper surface of the molten steel may be coated with slag before or after the supply of the zinc compound. This prevents the upper surface of the molten steel from coming into contact with an ambient air and can retard the evaporation of zinc after the decomposition.
- Usual methods for preparing the slag and usual composition of the slag may be used, but a suitable method described later may be also used.
- an oxide of calcium is supplied to the molten steel:
- the oxide of calcium is used for forming a slag in a steel smelting process.
- the upper surface of the molten steel is covered with the slag of the calcium oxide, and is prevented from contact with an ambient air. This retards the evaporation of zinc in the molten steel even if a long time is passed after the addition of zinc.
- the oxide of calcium may be supplied to the molten steel in a period when sufficient added zinc remains in the molten steel, and before or after the supply of the zinc compound.
- the calcium oxide may be supplied at the same time of supplying of the zinc compound by mixing and/or combining with the zinc compound. It is preferable that the calcium oxide is in an amount of 10 to 50 mass% of the total of the calcium oxide and the zinc compound, when the calcium oxide is mixed and/or combined with the zinc compound.
- the amount of the calcium oxide is too large, a melting point of the zinc compound at the time of the supply is lowered to facilitate the decomposition of the zinc compound. As a result, zinc generated by the decomposition evaporates faster.
- calcium fluoride (CaF 2 ) increases a fluidity of a slag, a part of the calcium oxide may be placed with the calcium fluoride to be supplied to the molten steel.
- the molten steel is for a hot work tool steel:
- Toughness of a hot work tool steel can be improved by adding zinc during a melting step of the hot work tool steel with use of the method of the present invention (see Patent Literature 1). Therefore, the method of the present invention is suitable for adding zinc to molten steel for a hot work tool steel. It is more preferable that a cast steel for the hot work tool steel includes not lower than 0.001 mass% of zinc.
- a hot work tool steel the elements defined in Standard steel grades in JIS etc. ,those elements described in Patent Literature 1, or those elements which have been proposed so far may be included according to necessary.
- JIS standard hot work tool steel SKD61 was prepared and the method for adding zinc according to the present invention was applied thereto.
- a chemical composition of the prepared SKD61 steel is shown in Table 1. (Ni, W, Zn, Nb and Co were not added.)
- the steel of Table 1 having a weight of 50 g of was melted in a MgO dense crucible in an electric furnace.
- a zinc compound (or a zinc metal) was directly supplied from the surface of the molten steel maintained at 1600°C in the following manner.
- the amount of zinc in the molten steel was calculated to be 1.0 mass% if the yield of zinc was 100% (hereinafter simply referred to as "calculated amount").
- the molten steel was maintained in an Ar atmosphere for a predetermined time.
- the molten steel was then water-cooled with the crucible to a room temperature.
- the zinc content in the solidified steel was analyzed to evaluate the yield of zinc.
- the analysis of the zinc content was conducted by the emission spectrometric analysis using spark discharge.
- Zinc aluminate powder represented by ZnO ⁇ Al 2 O 3 , having a stoichiometric composition of ZnO: 44.4 mass% and Al 2 O 3 : 55.6 mass%) was supplied to the molten steel.
- a zinc metal was supplied to the molten steel.
- a ZnO powder was supplied to the molten steel.
- Table 2 shows the zinc contents in the steel.
- Comparative Example 1 where a zinc metal was directly supplied to the molten steel, zinc started to evaporate immediately after the supply, and almost all of them evaporated after 30 minutes from the supply. Thus, the yield was poor.
- Comparative Example 2 where ZnO was used for the addition of zinc, the yield of zinc was improved compared to Comparative Example 1. However, ZnO was decomposed of rapidly after the supply, and almost all of the zinc components generated from the decomposition evaporated after 30 minutes. Thus, the yield was poor.
- Examples 1 and 2 where the method for adding zinc of the present invention was used, the yield of zinc was greatly improved. When the molten steel was cast after a predetermined time, it was found that a steel including not lower than .001 mass% of zinc could be produced.
- Example 2 Comparing between Examples 1 and 2, an upper surface of the molten steel was covered with slag after the supply in Example 2 where CaO was mixed to the zinc compound, and the zinc content in the molten steel after 10 minutes and 30 minutes were smaller than those in Example 1.
- Example 2 since CaO was mixed to the zinc compound, the melting point of the zinc compound was more or less lowered at the time of the supply, and therefore the zinc compound after the supply was decomposed faster than in Example 1. It is considered that the decomposition of the zinc compound progressed within a few minutes after the supply under the condition of Example 1 where the total amount of the molten steel was as low as 50 g. Thus, it is assumed that more zinc was present in the molten steel of Example 2 than in Example 1 in a few minutes after the supply.
- Fe - 15 mass% Ni alloy steel was prepared and the method according to the present invention was applied thereto.
- the chemical composition of the above alloy steel is shown in Table 3. (Cr, Mo, W, V, Zn, Nb and Co were not added.)
- the alloy steel of Table 1 having a weight of 25 tons was melted in an electric furnace and tapped into a ladle. Subsequently, the ladle with the molten steel was moved to the secondary refining equipment. A zinc compound was supplied to the molten steel maintained at 1600°C in the ladle, in a calculation amount such that the zinc content in the molten steel was 0.036 mass%. The molten steel was maintained for a predetermined time in an Ar atmosphere. The supplied zinc compound was mixed powder composed of 90 mass% of zinc aluminate powder and 10 mass% of CaO powder which is used in Example 2. The zinc compound was directly supplied to the molten steel.
- JIS standard hot work tool steel SKD61 was prepared and the method according to the present invention was applied thereto.
- the chemical composition of SKD61 is shown in Table 5. (Ni, W, Zn, Nb or Co was not added.)
- the steel of Table 5 having a weight of 25kg was melted in a high frequency induction furnace.
- a zinc compound was directly supplied to the molten steel maintained at 1600°C in the following manner, in a calculation amount such that the zinc content in the molten steel was 0.5 mass%.
- the molten steel was maintained for a predetermined time in an Ar atmosphere. Samples were taken from the top of the ladle using an iron mold at every given time period. Zinc contents of the samples were analyzed to evaluate the yield of zinc.
- the zinc contents were analyzed by emission spectrometric analysis using inductively coupled plasma.
- the zinc aluminate powder (ZnO ⁇ Al 2 O 3 ) which was used in Example 1 was supplied to the molten steel.
- a zinc silicate powder (represented by 2ZnO ⁇ SiO 2 , having a stoichiometric composition of ZnO: 71.6 mass% and SiO 2 : 28.4 mass%) was supplied to the molten steel.
- a ZnO powder was supplied to the molten steel.
- Table 6 shows the zinc contents in the steel. Table 6 also shows the state of fuming visually observed after the supply of the zinc compound.
- Comparative Example 3 where ZnO was supplied to the molten steel, the decomposition of ZnO progressed rapidly immediately after the supply, and the zinc component generated by the decomposition evaporated at an early stage. Thus, the yield of zinc was poor. Due to strong fuming, the test was abandoned after 10 minutes.
- Examples 4 to 6 where the method according to the present invention was used, the zinc compound continued to decompose even after 10 minutes from the supply of the zinc compound. The amount of zinc in the molten steel further increased after 30 minutes, showing a remarkable improvement in the yield of zinc. It has been found that a steel containing not lower than 0.001 mass% of zinc can be produced when the molten steel is subjected to casting after a predetermined time.
- Examples 4 to 6 are compared.
- Examples 4 and 5 where zinc aluminate was supplied to the molten steel, the reduction reaction immediately after the supply was further suppressed, and fuming was hardly observed throughout the retention time.
- Example 5 where CaO was mixed to zinc aluminate, the upper surface of the molten steel was covered with slag after the supply, and the amounts of zinc in the molten steel after 10 minutes and 30 minutes were greater than those in Example 4.
- Example 6 where zinc silicate was supplied to the molten steel, the zinc compound decomposed faster than in Examples 4 and 5, and the zinc content after a predetermined time is higher than those in Examples 4 and 5.
- a Fe - 6 mass% Cr alloy steel was prepared and the method according to the present invention was applied thereto.
- the chemical composition of the above alloy steel is shown in Table 7. (Ni, W, Zn, Nb and Co were not added.)
- the alloy steel of Table 7 having a weight of 25 tons was melted in an electric furnace and tapped into a ladle. Subsequently, the ladle with the molten steel was moved to a secondary refining equipment. A zinc compound was supplied to the molten steel maintained at 1600°C in the ladle, in a calculation amount such that the zinc content in the molten steel was 0.036 mass%. The molten steel was maintained for a predetermined time in an Ar atmosphere. The supplied zinc compound was the mixed powder composed of 90 mass% of zinc aluminate powder and 10 mass% of CaO powder used in Example 2. The zinc compound was directly supplied to the molten steel.
- Example 7 Samples of the molten steel were taken from the top of the ladle at every given time periods using an iron mold, and a final sample was taken from a runner after casting by a bottom pouring method.
- the zinc content of the samples was measured. Based on the analysis, a change of the zinc content in the molten steel after the supply of the zinc compound was determined.
- the zinc contents were analyzed by emission spectrometric analysis using inductively coupled plasma. Table 8 shows the zinc contents in the steel.
- Example 7 where the method of the present invention was employed, the yield of zinc was good and a high zinc content was maintained even 80 minutes after the supply of the zinc compound. Little fuming was visually observed after the supply of the zinc compound.
- the present invention can be applied to the manufacture of various steel materials including zinc, and can also be used for adding zinc to Ni or Cr metal, an alloy including such metal as a main component or the like.
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JP2011078118 | 2011-03-31 | ||
PCT/JP2011/079350 WO2012132138A1 (ja) | 2011-03-31 | 2011-12-19 | 溶鋼への亜鉛添加方法および亜鉛添加鋼の製造方法 |
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EP (1) | EP2695953B1 (zh) |
JP (1) | JP5761335B2 (zh) |
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RU2396364C1 (ru) * | 2009-04-15 | 2010-08-10 | ООО "Промышленная компания "Вторалюминпродукт" | Флюс для раскисления, рафинирования, модифицирования и легирования стали |
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EP0015417B1 (de) * | 1979-02-23 | 1983-04-13 | Mobay Chemical Corporation | Feinteiliges Verschlackungsmittel und Verfahren zum Stranggiessen von Stahl |
SU1468921A1 (ru) * | 1987-04-14 | 1989-03-30 | Уральский политехнический институт им.С.М.Кирова | Шлакообразующа смесь дл разливки сплавов на основе меди |
JPH0261006A (ja) * | 1988-08-25 | 1990-03-01 | Hitachi Cable Ltd | 製鋼用添加剤 |
FR2753205B1 (fr) * | 1996-09-12 | 1998-12-04 | Usinor Sacilor | Procede pour realiser un laitier moussant au-dessus d'un acier inoxydable en fusion dans un four electrique |
JP2003171714A (ja) * | 2001-12-07 | 2003-06-20 | Nippon Steel Corp | 溶鋼の精錬方法 |
JP4692282B2 (ja) * | 2003-10-08 | 2011-06-01 | 日立金属株式会社 | 鋼塊の製造方法 |
KR100711410B1 (ko) * | 2004-12-09 | 2007-04-30 | 가부시키가이샤 고베 세이코쇼 | 연성이 높은 박강판 및 그 제조방법 |
JP5029942B2 (ja) | 2006-01-30 | 2012-09-19 | 日立金属株式会社 | 靭性に優れた熱間工具鋼 |
JP5194586B2 (ja) * | 2006-07-05 | 2013-05-08 | 新日鐵住金株式会社 | 亜鉛めっき鋼板溶接用ステンレス鋼フラックス入り溶接ワイヤ |
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WO2009020890A1 (en) * | 2007-08-07 | 2009-02-12 | Dow Corning Corporation | Method of producing metals and alloys by carbothermal reduction of metal oxides |
CN101397616A (zh) * | 2008-06-26 | 2009-04-01 | 肖明 | 低燃点非金属元素和/或低熔点金属元素与高熔点金属元素熔融的方法 |
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JP5761335B2 (ja) | 2015-08-12 |
CN103443297A (zh) | 2013-12-11 |
WO2012132138A1 (ja) | 2012-10-04 |
TW201239104A (en) | 2012-10-01 |
CN103443297B (zh) | 2015-11-25 |
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