WO2022139313A1 - 법랑용 강판 및 그 제조방법 - Google Patents
법랑용 강판 및 그 제조방법 Download PDFInfo
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- WO2022139313A1 WO2022139313A1 PCT/KR2021/019113 KR2021019113W WO2022139313A1 WO 2022139313 A1 WO2022139313 A1 WO 2022139313A1 KR 2021019113 W KR2021019113 W KR 2021019113W WO 2022139313 A1 WO2022139313 A1 WO 2022139313A1
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 137
- 239000010959 steel Substances 0.000 title claims abstract description 137
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- 239000000037 vitreous enamel Substances 0.000 title abstract 3
- 239000010960 cold rolled steel Substances 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 210000003298 dental enamel Anatomy 0.000 claims description 141
- 238000000034 method Methods 0.000 claims description 40
- 238000000137 annealing Methods 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000010304 firing Methods 0.000 claims description 21
- 238000005098 hot rolling Methods 0.000 claims description 20
- 238000005096 rolling process Methods 0.000 claims description 19
- 230000009467 reduction Effects 0.000 claims description 18
- 238000005097 cold rolling Methods 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 238000004534 enameling Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 42
- 230000007547 defect Effects 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 33
- 241000251468 Actinopterygii Species 0.000 description 23
- 239000000463 material Substances 0.000 description 21
- 239000011572 manganese Substances 0.000 description 19
- 239000011651 chromium Substances 0.000 description 18
- 230000008569 process Effects 0.000 description 17
- 239000010949 copper Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 238000003860 storage Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009749 continuous casting Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 238000009628 steelmaking Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 230000002950 deficient Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008467 tissue growth Effects 0.000 description 1
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- 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
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- 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
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
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- 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
- C21D6/002—Heat treatment of ferrous alloys containing Cr
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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- 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
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- 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
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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- 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
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- 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
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- 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
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- 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
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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
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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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- 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
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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
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
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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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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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
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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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
Definitions
- One embodiment of the present invention relates to a steel sheet for enamel and a method for manufacturing the same. More specifically, an embodiment of the present invention relates to a continuous annealing-type steel sheet for enamel and a manufacturing method having excellent fish scale resistance and enamel adhesion, and also excellent yield strength even after enamel treatment.
- Enamel steel sheet is a type of surface treatment product that improves corrosion resistance, weather resistance, heat resistance, etc. by applying a glassy glaze on a base steel sheet such as a hot rolled steel sheet or a cold rolled steel sheet and then firing it at a high temperature.
- This enamel steel sheet is used for exterior construction, home appliances, tableware, and various industrial materials.
- Rimde steel has been used for enameling since ancient times, but as continuous casting has been actively used in terms of productivity improvement, most materials are being continuously cast.
- fishscale defects which are one of the most fatal defects of enamel steel sheets in steel manufacturing, are hydrogen dissolved in the steel during the manufacturing process of enamel products and become supersaturated in the steel during the cooling process after firing and then spread to the surface of the steel. It is a typical enamel defect caused by the enamel layer falling off in the shape of meat scales as it is released. When such a fish-scale defect occurs, it is necessary to suppress the occurrence because it greatly reduces the value of the enamel product, such as rust intensively in the defective area.
- OCA Open Coil Annealing
- TiN titanium nitride
- inclusions during the continuous casting stage of the steelmaking process. This frequently occurs, which is a direct factor in deterioration of workability and production load.
- TiN mixed in the molten steel is present on the top of the steel sheet and not only causes blister defects, which are typical bubble defects, but also a large amount of titanium is a factor that inhibits the adhesion between the steel sheet and the glaze layer.
- An embodiment of the present invention is to provide a steel sheet for enamel and a method for manufacturing the same. More specifically, in an embodiment of the present invention, it is an object of the present invention to provide a continuous annealing steel sheet for processing and a manufacturing method that does not cause bubble defects after enamel treatment and has excellent enamel adhesion and fish scale resistance.
- the steel sheet for enamel according to an embodiment of the present invention, in weight%, C: 0.0005 to 0.0030%, Mn: 0.15 to 0.55%, Si: 0.001 to 0.03%, Al: 0.0001 to 0.002%, P: 0.001 to 0.020% %, S: 0.001 to 0.030%, Cu: 0.02 to 0.06%, N: 0.005 to 0.012%, Cr: 0.05 to 0.20%, and O: 0.03 to 0.06%, and the remainder Fe and unavoidable impurities.
- the steel sheet for enamel according to an embodiment of the present invention includes an oxide layer in an inward direction from the surface, and the oxide layer thickness is 0.006 to 0.030 ⁇ m.
- the steel sheet for enamel according to an embodiment of the present invention may satisfy Equation 1 below.
- the steel sheet for enamel according to an embodiment of the present invention may satisfy Equation 2 below.
- Ti 0.001% by weight or less, Nb; 0.001 wt% or less, Ni: 0.02 wt% or less, V: 0.001 wt% or less, and Mo: 0.02 wt% or less may further include one or more.
- the steel sheet for enamel according to an embodiment of the present invention may satisfy Equation 3 below.
- Equation 3 P c represents the number of surface irregularities per unit centimeter (cm), R a represents the average roughness value ( ⁇ m), and S e represents the temper reduction ratio (%).
- the steel sheet for enamel according to an embodiment of the present invention may have a yield strength of 220 MPa or more after enamel plastic heat treatment.
- the steel sheet for enamel according to an embodiment of the present invention may have enamel adhesion of 95% or more.
- the steel sheet for enamel according to an embodiment of the present invention may have a hydrogen permeation ratio of 600 seconds/mm 2 or more.
- the annealing step may be performed for 10 to 90 seconds at a temperature of 760 to 840 °C.
- the finish hot rolling temperature may be 910 to 970 °C.
- the coiling temperature may be 580 to 720 °C.
- the rolling reduction may be 60 to 90%.
- the temper rolling may be performed at a reduction ratio of 0.4 to 2.0%.
- the step of enamel-sintering the temper-rolled steel sheet at a temperature of 780 to 850° C. may be further included.
- the steel sheet for enamel according to an embodiment of the present invention has excellent fish scale resistance and enamel adhesion.
- the steel sheet for enamel according to an embodiment of the present invention was able to maintain high adhesion by optimizing the surface roughness characteristics in the heat treatment and temper rolling steps in a continuous annealing furnace after cold rolling.
- the steel sheet for enamel according to an embodiment of the present invention can prevent fish scale defects caused by hydrogen by forming Mn-Cr-based precipitates at high temperatures and using them as a hydrogen storage source.
- residual nitrogen in the surface layer of the steel sheet suppresses grain growth during enamel firing, thereby securing stable material properties even after high-temperature firing.
- FIG. 1 is a schematic diagram of a cross-section of a steel sheet for enamel according to an embodiment of the present invention.
- first, second and third are used to describe, but are not limited to, various parts, components, regions, layers and/or sections. These terms are used only to distinguish one part, component, region, layer or section from another part, component, region, layer or section. Accordingly, a first part, component, region, layer or section described below may be referred to as a second part, component, region, layer or section without departing from the scope of the present invention.
- % means weight %, and 1 ppm is 0.0001 weight %.
- the meaning of further including the additional element means that the remaining iron (Fe) is included by replacing the additional amount of the additional element.
- the steel sheet for enamel according to an embodiment of the present invention, in weight%, C: 0.0005 to 0.0030%, Mn: 0.15 to 0.55%, Si: 0.001 to 0.03%, Al: 0.0001 to 0.002%, P: 0.001 to 0.020% %, S: 0.001 to 0.030%, Cu: 0.02 to 0.06%, N: 0.005 to 0.012%, Cr: 0.05 to 0.20%, O: 0.03 to 0.06%, and the balance Fe and unavoidable impurities.
- the content of the elements in the final steel sheet may have a concentration gradient in the thickness direction, and the element content, which will be described later, represents an average of the content in the entire steel sheet 100 including the oxide layer 20 .
- carbon (C) When carbon (C) is added too much, the amount of solid solution carbon in the steel increases, which prevents the development of texture after cold rolling and annealing, so workability may deteriorate. In addition, it may cause bubble defects due to bubbling of the enamel layer after enamel treatment. On the other hand, if C is too small, the tissue grows and the target yield strength cannot be secured after firing, and the fraction of precipitates acting as a hydrogen storage source is also lowered, so there is a problem that is vulnerable to fish scale defects. More specifically, carbon may include 0.0010 to 0.0028 wt%.
- Manganese (Mn) is a representative solid solution strengthening element, and by precipitating sulfur dissolved in steel in the form of manganese sulfide (MnS), it prevents hot shortness and promotes precipitation of carbides. If too little Mn is added, it is difficult to sufficiently obtain the above-described effect. On the other hand, if the content of Mn is too large, the moldability is deteriorated and the Ar 3 transformation temperature is lowered, which may cause a problem in that transformation occurs during enamel firing and deformation occurs. Accordingly, Mn may be included in an amount of 0.15 to 0.55% by weight. More specifically, it may contain 0.20 to 0.55 wt% of Mn.
- Si is an element that promotes solid solution strengthening and formation of carbides serving as a hydrogen storage source. When too little Si is added, it is difficult to sufficiently obtain the above-described effect. On the other hand, when Si is added too much, a high concentration of oxide film may be formed on the surface of the steel sheet to deteriorate the enamel adhesion. Accordingly, Si may be included in an amount of 0.001 to 0.030 wt%. More specifically, it may contain 0.005 to 0.025 wt%.
- Aluminum (Al) is used as a powerful deoxidizer to remove oxygen from molten steel in the steelmaking stage, and is an element that fixes dissolved nitrogen. Since it is necessary to utilize the precipitates and inclusions in the cavity to be used as a hydrogen storage source, possible deoxidation can be suppressed. Therefore, the upper limit of Al may be limited to 0.0020 wt%. Since it is desirable to contain as little Al as possible, the lower limit thereof may be limited to 0.0001% by weight. More specifically, it may include 0.0005 to 0.0015 wt% of Al.
- Phosphorus (P) is a representative material strengthening element. When too little P is added, it is difficult to sufficiently obtain the above-described effect. On the other hand, if too much P is added, a P segregation layer is formed inside the steel sheet, which not only reduces the formability, but also deteriorates the pickling property of the steel, which may adversely affect the enamel adhesion. Accordingly, P may be included in the range of 0.001 to 0.020 wt%. More specifically, it may contain 0.005 to 0.015 wt%.
- S Sulfur
- S is an element that combines with manganese to cause red hot brittleness. If S is added too little, a problem of worsening weldability may occur. When too much S is added, ductility is greatly reduced, which not only deteriorates workability, but also excessively precipitates manganese sulfide, which may adversely affect fish-scale properties of the product. Accordingly, S may be included in an amount of 0.001 to 0.030 wt%. More specifically, it may contain 0.005 to 0.025 wt%.
- Copper (Cu) is an element added to enhance solid solution strengthening and enamel adhesion. If too little Cu is added, the above-mentioned effect cannot be properly obtained. If too much Cu is added, the pickling rate is lowered in the acid treatment step, which is the enamel pretreatment process, so that proper roughness characteristics of the surface of the steel sheet cannot be obtained, thereby reducing adhesion. Accordingly, it may contain 0.020 to 0.060 wt% of Cu. More specifically, it may contain 0.025 to 0.055 wt%.
- N Nitrogen
- N is a typical hardening element and is added to obtain a target yield strength after enamel firing. If N is included too little, the yield strength after enamel firing may deteriorate. If too much N is included, moldability may deteriorate and surface defects such as bubble defects may occur in the enamel treatment process. Accordingly, it may contain 0.0050 to 0.0120 wt% of N. More specifically, it may include 0.0075 to 0.0110 wt%.
- Chromium (Cr) is an effective element for improving strength and fish scale resistance by forming precipitates and inclusions in the steel. If too little Cr is added, the above-mentioned effect cannot be properly obtained. When Cr is included too much, it may be concentrated on the surface to decrease the enamel adhesion and act as a cost increase factor due to the addition of expensive ferroalloy. Accordingly, it may contain Cr in an amount of 0.050 to 0.200 wt%. More specifically, it may include 0.075 to 0.190 wt%.
- Oxygen (O) is an essential element in forming oxides in steel, and these oxides act as an efficient hydrogen storage source to improve fish scale resistance. When too little O is contained, the above-described effect cannot be properly obtained. When O is included too much, it may cause dissolution loss of the refractory material in the steel sheet manufacturing step, as well as increase the occurrence of surface defects such as black lines on the surface of the steel sheet. Accordingly, O may include 0.0300 to 0.0600 wt%.
- the oxide layer 20 may be formed during an annealing process. However, since the thickness of the oxide layer 20 is very thin compared to the entire steel sheet 100 , there is substantially no change in the amount of oxygen in the entire steel sheet 100 .
- oxygen is included in 5 wt% or more. More specifically, 10 to 50 wt% of O may be included in the oxide layer 20 .
- the oxygen content in the oxide layer 20 means an average content in the oxide layer 20 .
- the steel sheet for enamel according to an embodiment of the present invention may satisfy Equation 1 below.
- Equation 1 If the value of Equation 1 is too low, proper surface properties cannot be secured in the pretreatment step, so the wedge effect is reduced, which may cause a problem in that the enamel adhesion is lowered. Conversely, if the value of Equation 1 is too high, the surface roughness properties disappear and the enamel glaze layer flows down, as well as the gas flow into the surface increases, causing frequent occurrence of enamel surface defects such as bubble defects, which can act as a factor reducing product reliability. have. Accordingly, in order to secure enamel adhesion and suppress surface bubble defects, the value of Equation 1 may be limited to 3.05 to 5.10. More specifically, the value of Equation 1 may be 3.20 to 5.00.
- the steel sheet for enamel according to an embodiment of the present invention may satisfy Equation 2 below.
- Equation 2 In the case of chromium and manganese in steel, it reacts with carbon, nitrogen, sulfur, etc. to form carbonitrides or acts as a complex precipitation source of these precipitates to improve workability and serve as a hydrogen storage source. Since it is necessary to consider the reactivity of Equation 2, the value of Equation 2 can be limited. If the value of Equation 2 is too small, too low may cause deterioration of workability as the amount of dissolved elements remaining in the steel increases. If the value of Equation 2 is too large, the rolling and annealing marketability may deteriorate as well as increase the manufacturing cost. Accordingly, the value of Equation 2 may be 0.0320 to 0.0910. More specifically, it may be 0.033 to 0.089.
- the present invention contains Fe and unavoidable impurities. Addition of effective ingredients other than the above ingredients is not excluded. Ti, Nb, Ni, V, Mo, etc. are mentioned as an unavoidable impurity. In an embodiment of the present invention, Ti, Nb, Ni, V, Mo, etc. are not intentionally added, Ti: 0.001 wt% or less, Nb: 0.001 wt% or less, Ni: 0.02 wt% or less, V: 0.001 wt% or less or less and Mo: may further include one or more of 0.02 wt% or less.
- FIG. 1 shows a schematic diagram of a cross-section of a steel sheet for enamel according to an embodiment of the present invention.
- an oxide layer 20 is included in an inward direction from the surface of the steel sheet.
- the oxide layer 20 is distinguished from the steel plate substrate 10 containing less than 5 wt% of oxygen (O) in that it contains 5 wt% or more of oxygen (O).
- O oxygen
- the oxide layer 20 and the substrate 10 are divided based on the point containing 5 wt% of oxygen.
- the innermost point is divided as a starting point.
- the oxide layer 20 may include 90 wt% or more of Fe oxide.
- the main component of the glaze is made of silicon-oxide (SiO 2 ), and in order to prevent deterioration of adhesion with the steel plate, an expensive glaze containing a large amount of NiO among the glaze components is often applied.
- the thickness of the oxide layer 20 on the surface of the steel sheet was limited to 0.006 to 0.030 ⁇ m. More specifically, the oxide layer 20 may have a thickness of 0.007 to 0.028 ⁇ m.
- the thickness of the oxide layer 20 may be different throughout the steel sheet 100 , and in one embodiment of the present invention, the thickness of the oxide layer 20 means an average thickness of the entire steel sheet 100 .
- the steel sheet for enamel according to an embodiment of the present invention may satisfy Equation 3 below.
- Equation 3 P c represents the number of surface irregularities per unit centimeter (1 cm), R a represents the average roughness value ( ⁇ m), and S e represents the temper reduction ratio (%).
- Equation 3 If the value of Equation 3 is small, the wedge effect on the surface of the steel plate may decrease and the adhesion with the glaze may be deteriorated. On the other hand, when the value of Equation 3 is too large, it may be difficult to secure the target material and enamel characteristics because the grains of the steel sheet grow after the enamel firing treatment. More specifically, the value of Equation 3 may be 0.4600 to 0.9500.
- the steel sheet for high-strength enamel having excellent adhesion according to the present invention may have excellent enamel adhesion while having excellent strength characteristics.
- the high-strength enamel steel sheet having excellent adhesion according to an embodiment of the present invention may have a yield strength of 220 MPa or more after enamel firing heat treatment.
- the yield strength of materials used for structural members is a physical property that influences dent resistance and shape freezeability of members, and is usually measured by the tensile test method.
- the yield strength of the products produced and supplied by steel companies is also important, but due to the characteristics of the product, after enamel glazing, it undergoes plastic heat treatment at high temperature to dry it. At this time, the heat treatment may be changed depending on the type of glaze used, but may be performed at a temperature of 780 to 850° C. for 15 minutes.
- the characteristics of enamel products were limited to 220 MPa or more because the yield strength after heat treatment in the enamel treatment process is a major factor in product stability review. Since the yield strength measured by the tensile test method is a property that can vary somewhat depending on the test conditions, in this evaluation, the cross head speed representing the tensile speed per unit time was applied at 10 mm per minute. The yield strength after enamel plastic heat treatment obtained through this may be 220 MPa or more, and more specifically, 225 MPa or more. At this time, the upper limit of the yield strength is not particularly limited, but may be, for example, 350 MPa.
- the enamel adhesion of the steel sheet for enamel according to an embodiment of the present invention may be 95% or more. By satisfying these properties, it can be applied as a material for enamel even using a relatively inexpensive glaze. If the adhesion to the enamel is too low, the glaze layer falls off during the distribution or handling process after enamel treatment, and the marketability as an enamel material deteriorates. As it acts as a factor in the rise, efforts are being made to come up with a way to secure enamel adhesion even with low-cost glazes. In general, if the enamel adhesion is 90% or more, it is classified as the best enamel product, but in one embodiment of the present invention, a method for securing the enamel adhesion of 95% or more is proposed.
- the enamel adhesion is low, the fish scale generation rate due to hydrogen increases in steel, so it is desirable to secure as high a adhesion as possible. More specifically, the enamel adhesion may be 96% or more.
- Enamel adhesion is a numerical value expressed by indexing the degree of enamel glaze drop-off by evaluating the degree of energization of the enamel layer after applying a certain load to the enamel layer with a steel ball as defined in the American Society for Testing and Materials standard, ASTM C313-78. .
- the upper limit of adhesion to enamel is not particularly limited, but may be, for example, 100%.
- the steel sheet for enamel according to an embodiment of the present invention may have a hydrogen permeation ratio of 600 seconds/mm 2 or more.
- Hydrogen permeability ratio is listed in European standard (EN10209) as a representative index for evaluating fish scale resistance, which shows resistance to fish scale defects, which is a fatal defect when applying enamel steel manufactured using cold rolled steel sheet according to an embodiment of the present invention
- the hydrogen permeation ratio is too low, after enamel treatment, accelerate heat treatment at 200°C for 24 hours to evaluate the resistance of fish scale defects. In order to secure the hydrogen permeation ratio, it is necessary to manage it at 600 sec/mm 2 or more. In addition, more specifically, the hydrogen permeation ratio may be 610 seconds/mm 2 or more. The upper limit of the hydrogen permeation ratio is not particularly limited, but may be, for example, 1700 seconds/mm 2 .
- a slab satisfying the above-described composition is prepared.
- Molten steel whose composition is adjusted to the above-mentioned composition in the steelmaking step can be manufactured into a slab through continuous casting.
- the alloy composition of the slab is substantially the same as the above-mentioned steel sheet for enamel. Since the alloy components have been described above, overlapping descriptions will be omitted.
- the manufactured slab Before hot rolling the slab, the manufactured slab may be heated. By heating, the subsequent hot rolling process can be smoothly performed, and the slab can be homogenized. More specifically, heating may mean reheating.
- the slab heating temperature may be 1150 to 1280 °C. If the slab heating temperature is too low, the rolling load may increase rapidly in the subsequent hot rolling process, which may deteriorate workability. On the other hand, if the slab heating temperature is too high, not only the energy cost increases, but also the amount of surface scale increases, which can lead to material loss. More specifically, it may be 1180 to 1260 °C.
- the heated slab is hot-rolled to manufacture a hot-rolled steel sheet.
- the finish rolling temperature of the hot rolling may be 910 to 970 °C. If the finish hot rolling temperature is too low, as rolling is finished in a low temperature region, crystal grains are rapidly mixed, which may lead to a decrease in rollability and workability. On the other hand, if the finish hot rolling temperature is too high, the peelability of the surface scale is deteriorated, and the impact toughness due to grain growth may be reduced as uniform hot rolling is not performed throughout the thickness. More specifically, the finish hot rolling temperature may be 920 to 960 °C.
- the hot-rolled steel sheet manufactured after hot rolling is subjected to a winding process. More specifically, it may be a hot-rolled winding process.
- the coiling temperature may be 580 to 720 °C.
- the hot-rolled steel sheet may be cooled in a run-out-table (ROT) before winding. If the hot-rolling temperature is too low, the widthwise temperature non-uniformity occurs in the cooling and maintaining process, which causes material deviation as the low-temperature precipitates are produced, and adversely affects the enamel. On the other hand, if the coiling temperature is too high, the corrosion resistance decreases as the agglomeration of the thinide progresses, and the cold rolling ductility decreases by promoting grain boundary segregation of P. occurred. More specifically, the coiling temperature may be 590 to 710 °C.
- the wound hot-rolled steel sheet may further include a step of pickling the steel sheet before cold rolling.
- the wound hot-rolled steel sheet is manufactured into a cold-rolled steel sheet through cold rolling.
- the cold rolling reduction may be 60 to 90%. If the cold rolling reduction ratio is too low, as the recrystallization driving force in the subsequent heat treatment process is not secured, non-recrystallized grains remain locally, increasing the strength, but there is a problem in that the workability is remarkably deteriorated. In addition, as the crushing ability of the carbide formed in the hot rolling step decreases, the number of sites that can occlude hydrogen is reduced, making it difficult to secure fish scale resistance. there was. On the other hand, if the cold rolling reduction ratio is too high, the material is hardened and workability is deteriorated, as well as the load of the rolling mill increases, thereby deteriorating the operability. More specifically, the cold rolling reduction may be 63 to 88%.
- the cold-rolled steel sheet may be annealed to manufacture an annealed steel sheet, and in this case, the annealing treatment may refer to a continuous annealing treatment.
- Cold rolled material has high strength due to high deformation applied in cold rolling, but extremely poor workability.
- the annealing temperature may be 760 to 840 °C, and the appropriate holding time may be 10 to 90 seconds.
- the annealing temperature may be 760 to 840 °C. If the annealing temperature is too low, the workability may be remarkably deteriorated as the deformation formed by cold rolling is not sufficiently removed. On the other hand, if the heat treatment temperature is too high, the annealing sheet-throughability may be deteriorated, such as increasing the possibility of plate breakage due to softening due to lowering of high-temperature strength. Therefore, the annealing temperature may be 760 to 840 °C. More specifically, the annealing temperature may be 770 to 830 °C.
- the holding time in the continuous annealing process may be 10 to 90 seconds. Even when the cracking time at the holding temperature was too short, unrecrystallized grains remained and acted as a factor that greatly deteriorated the formability. On the other hand, if the holding time was too long, crystal grain growth occurred and material softening occurred, and the subsequent process, firing Since it is difficult to secure a target material by heat treatment, the holding time at the annealing temperature may be 10 to 90 seconds. More specifically, it may be 15 to 80 seconds.
- the heat-treated steel sheet is temper rolled.
- temper rolling the shape of the material can be controlled and the desired surface roughness can be obtained, but if the temper reduction ratio is too high, the material is hardened by work hardening and the yield strength decreases rapidly due to tissue growth during subsequent plastic heat treatment, resulting in poor dent resistance. Since there is a problem that the temper rolling can be applied at a reduction ratio of 0.4 to 2.0%. More specifically, the rolling reduction of the temper rolling may be 0.5 to 1.8%.
- the step of enamel firing to dry the enamel-treated glaze may be further included.
- the enamel layer is applied to the surface of the steel sheet by heating it to high temperature and cooling it to room temperature.
- the firing temperature when the firing temperature is too high, it acts as a cost increase factor according to the increase of the energy source used, so the firing temperature can be applied at 780 to 850°C. More specifically, the firing temperature may be 790 to 840 °C.
- a slab passed through a converter ⁇ secondary refining ⁇ casting process was prepared with the composition of Table 1 below and the balance iron (Fe) and alloy components including unavoidable impurities.
- hot rolling was performed.
- the final thickness of the hot-rolled steel sheet was 4.0 mm.
- the hot-rolled specimen was subjected to cold rolling at a reduction ratio after removing the oxide film on the surface through pickling treatment. After cold rolling, the specimens were processed into enamel-treated specimens to investigate enamel properties and specimens for mechanical property analysis, and heat treatment was performed.
- the finish hot rolling temperature, coiling temperature, cold reduction ratio, annealing temperature, and holding time are summarized in Table 2 below.
- Table 3 below shows the operability, enamel, and tissue characteristics of the materials obtained through the above process for each manufacturing condition.
- Yield strength is the result obtained by performing a tensile test at a crosshead speed of 10 mm/min after producing a tensile test piece after calcination heat treatment at a temperature of 820 ° C for 15 minutes in a kiln to simulate the enamel glaze drying process for a steel sheet. .
- Enamel-treated specimens were cut to appropriate sizes for each application to meet the purpose of the test. After heat-treated specimens for enamel treatment were completely degreased, a standard glaze (check frit), which is relatively vulnerable to fish scale defects, was applied and maintained at 300°C for 10 minutes to retain moisture. was removed. After drying, the specimens were fired at each enamel firing temperature for 15 minutes to highlight the differences in enamel characteristics such as adhesion, and then cooled to room temperature. harsh conditions were chosen.
- Enamel adhesion which evaluates the adhesion between the steel plate and the glaze, is as defined in the American Society for Testing and Materials standard, ASTM C313-78. The degree was expressed as an index. In the present invention, the evaluation result of enamel adhesion was set as a goal of securing adhesion of 95% or more in terms of securing application stability in relatively inexpensive glazes.
- the hydrogen permeation ratio is one of the indexes to evaluate the resistance to fish scale, which is a fatal defect of enamel.
- hydrogen is generated in one direction of the steel sheet and hydrogen permeates to the other side. Measure out time (ts, unit: seconds), and it is expressed as the square of the material thickness (t, unit: mm), and is expressed as ts/t 2 (unit seconds/mm 2 ).
- Example 1 Invention lecture 1 930 680 75 780 30 1.4 0.8573 Invention example 2 Invention lecture 1 930 680 80 800 50 One 0.5875 Invention example 3 Invention lecture 1 930 680 85 820 70 0.6 0.4606 Invention Example 4 Invention lecture 2 925 620 70 790 40 1.5 0.9395 Invention Example 5 Invention lecture 2 925 620 85 810 60 0.8 0.5091 Invention example 6 Invention lecture 3 950 600 75 780 25 1.2 0.8703 Invention Example 7 Invention lecture 4 940 640 75 800 40 One 0.5733 Invention Example 8 Invention River 5 940 640 80 780 40 0.8 0.5667 Invention Example 9 Invention River 5 940 640 80 820 60 0.8 0.5761 Comparative Example 1 Invention lecture 1 750 680 80 650 50 One 0.3582 Comparative
- Inventive Examples 1 to 9 which satisfy all of the component composition, manufacturing conditions, and oxide layer thickness of the present invention, have good marketability as well as component ratios and related indices limiting the present invention range was satisfied, and enamel defects such as fish scale and bubble defects did not occur even under severe treatment conditions, and the hydrogen permeation ratio was 600 sec/mm 2 or higher, the enamel adhesion index was 95% or higher, and the yield strength after enamel firing heat treatment was 220 MPa or higher. Satisfied, it was possible to secure the properties targeted by the present invention.
- the annealing temperature was too low (Comparative Example 1), the annealing time was too short (Comparative Example 2), or the annealing temperature was too high (Comparative Example 3) , when the annealing time is too long (Comparative Example 4), the oxide layer thickness is too thin or too thick, and it can be confirmed that the enamel adhesion is less than 95%, or enamel defects such as bubble defects or fish scale occur after enamel treatment. It was not possible to secure the target properties as a whole, such as poor sheet-feeding properties, and in some cases, the yield strength after enamel firing was also less than 220 MPa.
- Example 2 shows the results of GDS analysis of the distribution of components in the thickness direction of the cold-rolled steel sheet for enamel according to Inventive Example 5; It was confirmed that the innermost point where the oxygen content was 5 wt% was 0.015 ⁇ m, and the oxide layer 20 having a thickness of 0.015 ⁇ m was present on the surface.
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Abstract
Description
구분 | C | Mn | Si | Al | P | S | N | Cu | O | Cr | 식 1 값 | 식 2 값 |
발명강1 | 0.0014 | 0.38 | 0.009 | 0.0006 | 0.009 | 0.009 | 0.0078 | 0.036 | 0.0364 | 0.108 | 4.00 | 0.067 |
발명강2 | 0.0018 | 0.29 | 0.007 | 0.0009 | 0.012 | 0.014 | 0.0092 | 0.055 | 0.0422 | 0.153 | 4.583 | 0.053 |
발명강3 | 0.0015 | 0.46 | 0.012 | 0.0005 | 0.011 | 0.011 | 0.0087 | 0.054 | 0.048 | 0.184 | 4.909 | 0.089 |
발명강4 | 0.0022 | 0.31 | 0.02 | 0.0006 | 0.008 | 0.017 | 0.0109 | 0.029 | 0.0534 | 0.098 | 3.625 | 0.049 |
발명강5 | 0.0026 | 0.24 | 0.024 | 0.0010 | 0.014 | 0.008 | 0.0105 | 0.046 | 0.0406 | 0.115 | 3.286 | 0.034 |
비교강1 | 0.0019 | 0.07 | 0.011 | 0.0380 | 0.008 | 0.010 | 0.0024 | 0.012 | 0.0013 | 0.173 | 1.50 | 0.006 |
비교강2 | 0.0027 | 0.68 | 0.015 | 0.0008 | 0.034 | 0.045 | 0.0035 | 0.053 | 0.0425 | 0.358 | 1.559 | 0.031 |
비교강3 | 0.0086 | 0.36 | 0.022 | 0.0005 | 0.015 | 0.011 | 0.0025 | - | 0.0381 | 0.91 | 0 | 0.007 |
비교강4 | 0.0025 | 0.54 | 0.011 | 0.0511 | 0.008 | 0.015 | 0.0099 | 0.042 | 0.0015 | 1.068 | 5.25 | 0.127 |
비교강5 | 0.0067 | 0.22 | 0.218 | 0.0013 | 0.067 | 0.021 | 0.0144 | 0.356 | 0.0151 | 0.082 | 5.313 | 0.016 |
구분 | 강종 No. |
마무리 열간 압연온도 (℃) |
권취 온도 (℃) |
냉간 압하율 (%) |
소둔 온도 (℃) |
유지 시간 (초) |
조질 압하율 (%) |
식 3 값 |
발명예1 | 발명강1 | 930 | 680 | 75 | 780 | 30 | 1.4 | 0.8573 |
발명예2 | 발명강1 | 930 | 680 | 80 | 800 | 50 | 1 | 0.5875 |
발명예3 | 발명강1 | 930 | 680 | 85 | 820 | 70 | 0.6 | 0.4606 |
발명예4 | 발명강2 | 925 | 620 | 70 | 790 | 40 | 1.5 | 0.9395 |
발명예5 | 발명강2 | 925 | 620 | 85 | 810 | 60 | 0.8 | 0.5091 |
발명예6 | 발명강3 | 950 | 600 | 75 | 780 | 25 | 1.2 | 0.8703 |
발명예7 | 발명강4 | 940 | 640 | 75 | 800 | 40 | 1 | 0.5733 |
발명예8 | 발명강5 | 940 | 640 | 80 | 780 | 40 | 0.8 | 0.5667 |
발명예9 | 발명강5 | 940 | 640 | 80 | 820 | 60 | 0.8 | 0.5761 |
비교예1 | 발명강1 | 750 | 680 | 80 | 650 | 50 | 1 | 0.3582 |
비교예2 | 발명강2 | 925 | 760 | 50 | 790 | 10 | 2.2 | 2.2611 |
비교예3 | 발명강3 | 950 | 460 | 75 | 900 | 50 | 1 | 0.3905 |
비교예4 | 발명강4 | 940 | 640 | 93 | 800 | 120 | 0.3 | 0.1269 |
비교예5 | 비교강1 | 930 | 640 | 75 | 800 | 40 | 2.1 | 3.255 |
비교예6 | 비교강2 | 930 | 640 | 75 | 800 | 40 | 0.8 | 0.3775 |
비교예7 | 비교강3 | 940 | 640 | 75 | 800 | 40 | 0.8 | 0.3138 |
비교예8 | 비교강4 | 940 | 640 | 75 | 800 | 40 | 0.8 | 0.3833 |
비교예9 | 비교강5 | 940 | 640 | 75 | 800 | 40 | 0.8 | 0.3556 |
구 분 | 통판성 | 산화층 두께 (㎛) |
가공성 | 항복강도 (㎫) |
기포 결함 발생 유무 |
피쉬스케일 발생 유무 |
법랑밀착성 (%) |
수소투과비 (초/㎟) |
발명예1 | O | 0.012 | O | 264 | O | O | 99.9 | 1026 |
발명예2 | O | 0.018 | O | 248 | O | O | 100 | 1249 |
발명예3 | O | 0.021 | O | 239 | O | O | 99.4 | 1135 |
발명예4 | O | 0.011 | O | 249 | O | O | 100 | 982 |
발명예5 | O | 0.015 | O | 292 | O | O | 99.9 | 894 |
발명예6 | O | 0.008 | O | 281 | O | O | 99.8 | 1014 |
발명예7 | O | 0.025 | O | 254 | O | O | 100 | 826 |
발명예8 | O | 0.019 | O | 245 | O | O | 99.7 | 924 |
발명예9 | O | 0.013 | O | 286 | O | O | 99.2 | 795 |
비교예1 | X | 0.002 | X | 217 | X | X | 84.2 | 526 |
비교예2 | X | 0.004 | O | 154 | X | X | 74.8 | 462 |
비교예3 | X | 0.033 | X | 121 | X | X | 92.6 | 551 |
비교예4 | X | 0.004 | X | 264 | X | X | 76.8 | 582 |
비교예5 | X | 0.003 | O | 168 | △ | X | 88.6 | 326 |
비교예6 | O | 0.003 | X | 179 | X | O | 64.2 | 572 |
비교예7 | X | 0.002 | X | 182 | X | X | 58.4 | 509 |
비교예8 | O | 0.001 | X | 209 | X | X | 77.3 | 274 |
비교예9 | X | 0.003 | X | 276 | X | X | 52.6 | 496 |
Claims (14)
- 중량%로, C: 0.0005 내지 0.0030%, Mn: 0.15 내지 0.55%, Si: 0.001 내지 0.03%, Al: 0.0001 내지 0.002%, P: 0.001 내지 0.02%, S: 0.001 내지 0.03%, Cu: 0.02 내지 0.06%, N: 0.005 내지 0.012%, Cr: 0.05 내지 0.20% 및 O: 0.03 내지 0.06% 포함하고, 잔부 Fe 및 불가피한 불순물을 포함하고,표면에서부터 내부 방향으로 산화층을 포함하고, 상기 산화층 두께가 0.006 내지 0.030㎛인 법랑용 강판.
- 제1항에 있어서,하기 식 1을 만족하는 법랑용 강판.[식 1]3.05 ≤ [Cu]/[P] ≤ 5.10(상기 식 1에서 [Cu] 및 [P]은 각각, Cu 및 P의 함량(중량%)을 나타낸다.)
- 제1항에 있어서,하기 식 2를 만족하는 법랑용 강판.0.032 ≤ ([Cr]/52 + [Mn]/32)×([N]/14) / ([C]/12) ≤ 0.091(상기 식 2에서 [Cr], [Mn], [N] 및 [C]은 각각, Cr, Mn, N 및 C의 함량(중량%)을 나타낸다.)
- 제1항에 있어서,Ti: 0.001 중량% 이하, Nb: 0.001 중량% 이하, Ni: 0.02 중량% 이하, V: 0.001 중량% 이하 및 Mo: 0.02 중량% 이하 중 1종 이상을 더 포함하는 법랑용 강판.
- 제1항에 있어서,하기 식 3을 만족하는 법랑용 강판.[식 3]0.45 ≤ (Ra×50×Se)/Pc ≤ 0.99(상기 식 3에서 Pc는 단위 센티미터(cm)당 표면 요철의 수를, Ra는 평균 조도값(㎛), Se는 조질압하율(%)을 나타낸다.)
- 제1항에 있어서,법랑 소성 열처리 후 항복강도가 220㎫ 이상인 법랑용 강판.
- 제1항에 있어서,법랑밀착성이 95% 이상인 법랑용 강판.
- 제1항에 있어서,수소투과비가 600초/mm2 이상인 법랑용 강판.
- 중량%로, C: 0.0005 내지 0.0030%, Mn: 0.15 내지 0.55%, Si: 0.001 내지 0.03%, Al: 0.0001 내지 0.002%, P: 0.001 내지 0.020%, S: 0.001 내지 0.030%, Cu: 0.02 내지 0.06%, N: 0.005 내지 0.012%, Cr: 0.05 내지 0.20% 및 O: 0.03 내지 0.06% 포함하고, 잔부 Fe 및 불가피한 불순물을 포함하는 슬라브를 열간 압연하여 열연강판을 제조하는 단계;상기 열연강판을 냉간압연하여 냉연강판을 제조하는 단계;상기 냉연강판을 소둔하는 단계; 및소둔된 상기 냉연강판을 조질 압연하는 단계를 포함하고,상기 소둔 단계는 760 내지 840℃의 온도하에서 10 내지 90초 동안 수행하고,법랑용 강판의 제조 방법.
- 제9항에 있어서,상기 열연 강판을 제조하는 단계에서,마무리 열간 압연 온도는 910 내지 970℃인 법랑용 강판의 제조 방법.
- 제9항에 있어서,상기 열연 강판을 제조하는 단계에서,권취 온도는 580 내지 720℃인 법랑용 강판의 제조 방법.
- 제9항에 있어서,상기 냉연 강판을 제조하는 단계에서 압하율이 60 내지 90%인 법랑용 강판의 제조 방법.
- 제9항에 있어서,상기 조질 압연은 압하율 0.4 내지 2.0%로 압연하는 법랑용 강판의 제조 방법.
- 제9항에 있어서,상기 조질 압연하는 단계 이후, 조질 압연된 강판을 780 내지 850℃의 온도 에서 법랑 소성하는 단계를 더 포함하는 법랑용 강판의 제조 방법.
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JP6683294B1 (ja) * | 2018-05-17 | 2020-04-15 | 日本製鉄株式会社 | 鋼板およびほうろう製品 |
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KR20090043570A (ko) * | 2006-09-19 | 2009-05-06 | 신닛뽄세이테쯔 카부시키카이샤 | 법랑 시유용 가공품, 법랑 가공품 |
KR101193300B1 (ko) * | 2006-09-27 | 2012-10-19 | 신닛뽄세이테쯔 카부시키카이샤 | 내피쉬스케일성이 우수한 에나멜용 강판, 내피쉬스케일성이 우수한 연속 주조 에나멜용 강편의 제조 방법 및 내피쉬스케일성이 우수한 연속 주조 에나멜용 강판의 제조 방법 |
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CN108796380B (zh) * | 2017-04-26 | 2020-06-23 | 宝山钢铁股份有限公司 | 烧成后屈服强度在210MPa以上的极低碳冷轧搪瓷用钢板及其制造方法 |
JP6683294B1 (ja) * | 2018-05-17 | 2020-04-15 | 日本製鉄株式会社 | 鋼板およびほうろう製品 |
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