EP3686306B1 - Steel plate and method for manufacturing same - Google Patents
Steel plate and method for manufacturing same Download PDFInfo
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- EP3686306B1 EP3686306B1 EP18858881.8A EP18858881A EP3686306B1 EP 3686306 B1 EP3686306 B1 EP 3686306B1 EP 18858881 A EP18858881 A EP 18858881A EP 3686306 B1 EP3686306 B1 EP 3686306B1
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- 229910000831 Steel Inorganic materials 0.000 title claims description 76
- 239000010959 steel Substances 0.000 title claims description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 5
- 239000000463 material Substances 0.000 claims description 32
- 238000005096 rolling process Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 238000005098 hot rolling Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 description 49
- 238000005260 corrosion Methods 0.000 description 49
- 230000000694 effects Effects 0.000 description 25
- 238000005336 cracking Methods 0.000 description 18
- 239000002244 precipitate Substances 0.000 description 16
- 229910001566 austenite Inorganic materials 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 239000010953 base metal Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 150000001247 metal acetylides Chemical class 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 238000009628 steelmaking Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000000877 morphologic effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000746 Structural steel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 2
- 238000010349 cathodic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- -1 salinity Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—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
- C21D8/0273—Final recrystallisation annealing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
-
- 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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
Definitions
- This invention relates to a steel plate that is suitable for structural steel used in an extremely low-temperature environment such as a storage tank of liquefied gas, in particular, a steel plate excellent in corrosion resistance in a salinity corrosive environment, and a method for manufacturing the same.
- the hot-rolled steel plate In using a hot-rolled steel plate in a structure for a storage tank of liquefied gas, the operating environment is at extremely low temperatures. Therefore, the hot-rolled steel plate needs to have not only high strength but also toughness at extremely low temperatures. For example, for a hot-rolled steel plate used for a storage tank of liquefied natural gas, excellent toughness needs to be guaranteed at the boiling point of liquefied natural gas, that is, -164 °C or lower. When a steel material has poor low-temperature toughness, the safety as a structure for an extremely low-temperature storage tank may not be maintained. Thus, there is a growing demand for steel materials with improved low-temperature toughness that are applied to such a structure.
- austenitic stainless steel which has an austenite microstructure exhibiting no brittleness at extremely low temperatures
- 9 % Ni steel, or five thousand series aluminum alloys have been conventionally used.
- the alloy cost and manufacturing cost of those metal materials are high, and thus there is a demand for steel plates which are inexpensive and excellent in extremely low-temperature toughness.
- high-Mn steel added with a large amount of Mn which is a relatively inexpensive austenite-stabilizing element to form an austenite microstructure is considered to be used as a structural steel plate used in an extremely low-temperature environment.
- JP 2015-508452 A (PTL 1) describes a steel material having improved machinability by cutting and Charpy impact properties at -196 °C of a weld heat-affected zone (HAZ) through addition of Mn in an amount of 15 % to 35 %, Cu in an amount of 5 % or less, and C and Cr in a suitable amount.
- HZ weld heat-affected zone
- JP 2016-84529 A (PTL 2) describes a high-Mn steel material having improved low temperature toughness through addition of C: 0.25 % to 0.75 %; Si: 0.05 % to 1.0 %; Mn: more than 20 % to 35 % or less; Ni: 0.1 % or more and less than 7.0 %; and Cr: 0.1 % or more and less than 8.0 %.
- JP 2016-196703 A (PTL 3) describes a high-Mn steel material having a base metal and a welded portion with improved extremely low-temperature toughness through addition of C in an amount of 0.001 % to 0.80 % and Mn in an amount of 15 % to 35 %, and addition of elements such as Cr, Ti, Si, Al, Mg, Ca, and REM.
- JP 2016 196703 A describes a high Mn steel for cryogenic use and a manufacturing method thereof
- JP 2016 084529 A describes a high-Mn steel material suitable for a material for storing liquefied gas and a method for producing the same.
- excellent in corrosion resistance means a fracture stress of 400 MPa or more when a test in accordance with the Slow Strain Rate Test Method based on NACE Standard TM0111-2011 is performed by immersing in artificial seawater (chloride ion concentration of 18000 ppm) at 23 °C and performing a constant-rate tensile test at a strain rate of 4 ⁇ 10 -7 inch/s.
- this invention it is possible to provide a steel plate excellent in corrosion resistance, in particular, corrosion resistance in a salinity corrosive environment. Therefore, when our steel plate is used for a steel structure used in an extremely low-temperature environment such as a tank for a storage tank of liquefied gas, the safety and the service life of the steel structure is significantly improved, thus producing significantly advantageous effects in industrial terms. Further, our steel plate is inexpensive compared with conventional materials, and thus excellent in economic efficiency.
- the C content is set to be 0.20 % or more and 0.70 % or less, and preferably 0.25 % or more and 0.60 % or less.
- Si 0.05 % or more and 1.00 % or less
- Si acts as a deoxidizer, is necessary for steelmaking, and is effective at increasing the strength of a steel plate by solid solution strengthening when dissolved in steel. To obtain such an effect, the Si content needs to be 0.05 % or more. On the other hand, a Si content beyond 1.00 % may deteriorate weldability and surface characteristics, lowering stress corrosion cracking resistance. Therefore, the Si content is set to 0.05 % or more and 1.00 % or less, and preferably 0.07 % or more and 0.50 % or less.
- Mn 15.0 % or more and 35.0 % or less
- Mn is a relatively inexpensive austenite-stabilizing element.
- Mn is an important element for achieving both high strength and extremely low-temperature toughness.
- the Mn content needs to be 15.0 % or more.
- the Mn content beyond 35.0 % causes saturation of the effect of improving the extremely low-temperature toughness, increasing alloy costs. Further, such a high Mn content deteriorates weldability and cuttability, and further promotes segregation as well as the occurrence of stress corrosion cracking. Therefore, the Mn content is set to 15.0 % or more and 35.0 % or less, and preferably 18.0 % or more and 28.0 % or less.
- the upper limit of the P content is 0.030 %, and desirably, the P content is kept as small as possible. Properties are improved as the P content is lower, and thus, the P content is preferably set to 0.024 % or less, and more preferably 0.020 % or less. On the other hand, reducing the P content to less than 0.001 % involves high steelmaking costs and impairs economic efficiency. Thus, the content of 0.001 % or more is allowable.
- the upper limit of the S content is 0.0200 %, and desirably, the S content is kept as small as possible. Therefore, the S content is set to 0.0200 % or less, and preferably 0.0180 % or less.
- reducing the S content to less than 0.0001 % involves high steelmaking costs and impairs economic efficiency. Thus, the content of 0.0001 % or more is allowable.
- Al 0.010 % or more and 0.100 % or less
- Al acts as a deoxidizer and is used most commonly in molten steel deoxidizing processes to obtain a steel plate.
- Al also has an effect of fixing solute N in steel to form AlN, thus suppressing coarsening of crystal grains.
- Al has an effect of suppressing deterioration of toughness caused by decrease in solute N.
- the Al content needs to be 0.010 % or more.
- a Al content beyond 0.100 % may form coarse nitrides which would become an origin of corrosion and fracture, thus lowering stress corrosion cracking resistance.
- Al diffuses to a weld metal portion during welding to deteriorate toughness of the weld metal.
- the Al content is set to 0.100 % or less, and preferably 0.020 % or more and 0.070 % or less.
- Cr is an important element because it is contained in a suitable amount to thereby produce an effect of delaying an initial corrosion reaction on a steel plate surface in a salinity corrosive environment to decrease the amount of hydrogen entering a steel plate and improve stress corrosion cracking resistance.
- the Cr content is increased, corrosion resistance can be improved.
- Cr inevitably precipitates in the form of, for example, a nitride, a carbide, or a carbonitride during rolling and those precipitates may become an origin of corrosion and fracture to deteriorate stress corrosion cracking resistance. Therefore, the Cr content is set to 0.5 % or more and 8.0 % or less.
- the amount of solute Cr is preferably 1.0 % or more and 6.0 % or less, and more preferably 1.2 % or more and 5.5 % or less.
- the solid solution state refers to a state in which solute atoms exist as atoms without forming precipitates.
- N 0.0010 % or more and 0.0300 % or less
- N is an austenite-stabilizing element and an element which is effective for improving extremely low-temperature toughness. Further, N has an effect of bonding with Nb, V, and Ti to finely precipitate as nitrides or carbonitrides and serving as a diffusible hydrogen trapping site to suppress stress corrosion cracking. To obtain such an effect, the N content needs to be 0.0010 % or more. On the other hand, a N content beyond 0.0300 % promotes the formation of excessive nitrides or carbonitrides to reduce the solute element amount, lowering not only corrosion resistance but also toughness. Therefore, the N content is set to 0.0010 % or more and 0.0300 % or less, and preferably 0.0020 % or more and 0.0150 % or less.
- the following elements can be contained as necessary: Nb: 0.003 % or more and 0.030 % or less and V: 0.01 % or more and 0.10 % or less, and Ti: 0.003 % or more and 0.040 % or less.
- Nb 0.003 % or more and 0.030 % or less
- Nb precipitates as carbonitrides and the formed carbonitrides serve as a diffusible hydrogen trapping site.
- Nb is an element which has an effect of suppressing stress corrosion cracking.
- Nb is preferably contained in an amount of 0.003 % or more.
- the Nb content is more than 0.030 %, coarse carbonitrides may precipitate to become an origin of fracture. Further, the precipitates may be coarsened to deteriorate base metal toughness.
- the Nb content is preferably set to 0.003 % or more and 0.030 % or less, more preferably 0.005 % or more and 0.025 % or less, and further preferably 0.007 % or more and 0.022 % or less.
- V 0.01 % or more and 0.10 % or less
- V precipitates as carbonitrides and the formed carbonitrides serve as a diffusible hydrogen trapping site.
- V is an element which has an effect of suppressing stress corrosion cracking.
- V is preferably contained in an amount of 0.01 % or more.
- the V content is more than 0.10 %, coarse carbonitrides may precipitate to become an origin of fracture. Further, the precipitates may be coarsened to deteriorate base metal toughness. Therefore, when V is contained, the V content is preferably set to 0.01 % or more and 0.10 % or less, more preferably 0.02 % or more and 0.09 % or less, and further preferably 0.03 % or more and 0.08 % or less.
- Ti precipitates as nitrides or carbonitrides and the formed nitrides or carbonitrides serve as a diffusible hydrogen trapping site.
- Ti is an element which has an effect of suppressing stress corrosion cracking.
- Ti is preferably contained in an amount of 0.003 % or more.
- the precipitates may be coarsened to deteriorate base metal toughness. Further, coarse carbonitrides may precipitate to become an origin of fracture.
- the Ti content is preferably set to 0.003 % or more and 0.040 % or less, more preferably 0.005 % or more and 0.035 % or less, and further preferably 0.007 % or more and 0.032 % or less.
- the chemical composition may optionally contain at least one selected from the group of Cu: 0.01 % or more and 0.50 % or less, Ni: 0.01 % or more and 0.50 % or less, Sn: 0.01 % or more and 0.30 % or less, Sb: 0.01 % or more and 0.30 % or less, Mo: 0.01 % or more and 2.0 % or less, and W: 0.01 % or more and 2.0 % or less.
- Cu, Ni, Sn, Sb, Mo, and W are elements which are added with Cr to thereby improve corrosion resistance of high-Mn steel in a salinity corrosive environment.
- Cu, Sn, and Sb have an effect of increasing hydrogen overvoltage in a steel material to thereby suppress a hydrogen evolution reaction corresponding to the cathodic reaction.
- Ni forms a precipitation layer on a steel material surface and physically suppresses permeation of corrosive anions such as Cl - into a steel substrate.
- Cu, Ni, Sn, Sb, Mo, and W are liberated as a metal ion from a steel material surface during corrosion and densify corrosion products, thereby suppressing permeation of corrosive anions into a steel interface (interface between a rust layer and a steel substrate).
- Mo and W are liberated as MO 4 2- and WO 4 2- , respectively, and adsorbed in the corrosive products or to the steel plate surface, thereby imparting cation selective permeability and electrically suppressing permeation of corrosive anions into the steel substrate.
- preferred contents are: a Cu content of 0.01 % or more and 0.50 % or less; a Ni content of 0.01 % or more and 0.50 % and less; a Sn content of 0.01 % or more and 0.30 % or less; a Sb content of 0.01 % or more and 0.30 % or less; a Mo content of 0.01 % or more and 2.0 % or less; and a W content of 0.01 % or more and 2.0 % or less.
- More preferred contents are: a Cu content of 0.02 % or more and 0.40 % or less; a Ni content of 0.02 % or more and 0.40 % or less; a Sn content of 0.02 % or more and 0.25 % or less; a Sb content of 0.02 % or more and 0.25 % or less; a Mo content of 0.02 % or more and 1.9 % or less; and a W content of 0.02 % or more and 1.9 % or less.
- the chemical composition may optionally contain at least one selected from the group of Ca: 0.0005 % or more and 0.0050 % or less, Mg: 0.0005 % or more and 0.0100 % or less, and REM: 0.0010 % or more and 0.0200 % or less.
- Ca, Mg, and REM are elements useful for morphological control of inclusions and can be contained as necessary.
- the morphological control of inclusions means granulating elongated sulfide-based inclusions.
- the morphological control of inclusions improves ductility, toughness, and sulfide stress corrosion cracking resistance.
- Ca and Mg are preferably contained in an amount of 0.0005 % or more and REM is preferably contained in an amount of 0.0010 % or more.
- the Ca content is preferably set to 0.0005 % or more and 0.0050 % or less
- the Mg content is preferably set to 0.0005 % or more and 0.0100 % or less
- the REM content is preferably set to 0.0010 % or more and 0.0200 % or less.
- a Ca content of 0.0010 % or more and 0.0040 % or less, a Mg content of 0.0010 % or more and 0.0040 % or less, and a REM content is 0.0020 % or more and 0.0150 % or less are more preferable.
- temperatures (°C) refer to the temperature of the mid-thickness part of a steel plate. [Reheating temperature of a steel raw material: 1000 °C or higher and 1300 °C or lower]
- Heating a steel raw material to 1000 °C or higher is for dissolving carbonitrides in the microstructure to make the crystal grain size and the like uniform. Specifically, when the heating temperature is lower than 1000 °C, carbonitrides are not sufficiently dissolved and thus desired properties cannot be obtained. Further, heating at a temperature higher than 1300 °C deteriorates material properties due to coarsening of crystal grain size and needs excessive energy, lowering productivity.
- the upper limit of the heating temperature is set to 1300 °C, preferably 1050 °C or higher and 1250 °C or lower, and more preferably 1070 °C or higher and 1250 °C or lower.
- the rolling reduction ratio in hot rolling is limited to 3 or more.
- the upper limit of the rolling reduction ratio needs to be 30 for the reasons given below.
- the rolling reduction ratio is defined by a plate thickness of a material to be rolled / a plate thickness of a steel plate after hot rolling.
- the finish rolling temperature is lower than 750 °C, the amount of carbide precipitates during rolling is significantly increased, and even when the time for which a material to be rolled resides within a temperature range of 600 °C to 950 °C is 30 minutes or less, a sufficient amount of solute Cr may not be obtained, lowering corrosion resistance. Further, when rolling is performed at a temperature of lower than 750 °C, deformation resistance is increased to apply an excessive load to a manufacturing apparatus.
- the finish rolling temperature is set to 750 °C or higher. From the viewpoint of suppressing significant coarsening of crystal grain size, the upper limit of the finish rolling temperature is preferably 1050 °C or lower.
- the time for which a material to be rolled resides within a temperature range of 600 °C to 950 °C (residence time) is more than 30 minutes, a large amount of carbonitrides and carbides precipitate during rolling and the necessary amount of solute Cr cannot be obtained, lowering corrosion resistance and extremely-low temperature toughness. Therefore, the time for which a material to be rolled resides within a temperature range of 600 °C to 950 °C is limited to 30 minutes or less.
- the time for which a material to be rolled resides within a temperature range of 600 °C to 950 °C is preferable as short as possible, and thus, no lower limit is placed thereon.
- the length of the material to be rolled is made to be 5000 mm or less and the rolling reduction ratio of the material to be rolled is limited to 30 or less as described above. This is because when the length of the material to be rolled is more than 5000 mm or the rolling reduction ratio is more than 30, the rolling time becomes long and as a result, the time for which a material to be rolled resides within a temperature range of 600 °C to 950 °C exceeds 30 minutes.
- the average cooling rate within a temperature range of 600 °C to 700 °C is less than 3 °C/s, a large amount of precipitates such as Cr carbides are formed, the average cooling rate is limited to 3 °C/s or more.
- the average cooling rate is preferable as fast as possible, and thus, no upper limit is placed thereon.
- Steels of Nos. 1 to 28 listed in Table 1 were produced by steelmaking to obtain slabs, subsequently the slabs were formed into steel plates of sample Nos. 1 to 34 having a plate thickness of 6 mm to 50 mm under the manufacturing conditions listed in Table 2, and the steel plates were subjected to the following test.
- the corrosion resistance test was performed in accordance with the Slow Strain Rate Test Method based on NACE Standard TM0111-2011 (hereinafter, referred to as "SSRT test"). Test pieces having a shape of notched Type A round bar were used. The test pieces were immersed in artificial seawater (having chloride ion concentration of 18000 ppm) at 23 °C and subjected to a constant-rate tensile test at a strain rate of 4 ⁇ 10 -7 inch/s. In this invention, a test piece having a fracture stress of 400 MPa or more was considered as having excellent stress corrosion cracking resistance. The results thus obtained are listed in Table 2. Table 2 Sample No. Material No.
- Example Nos. 1 to 17 were confirmed to have corrosion resistance satisfying 400 MPa or more for the fracture stress of the SSRT test.
- comparative examples outside the scope of this disclosure did not satisfy the above-described target performance in terms of stress corrosion cracking resistance.
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Description
- This invention relates to a steel plate that is suitable for structural steel used in an extremely low-temperature environment such as a storage tank of liquefied gas, in particular, a steel plate excellent in corrosion resistance in a salinity corrosive environment, and a method for manufacturing the same.
- In using a hot-rolled steel plate in a structure for a storage tank of liquefied gas, the operating environment is at extremely low temperatures. Therefore, the hot-rolled steel plate needs to have not only high strength but also toughness at extremely low temperatures. For example, for a hot-rolled steel plate used for a storage tank of liquefied natural gas, excellent toughness needs to be guaranteed at the boiling point of liquefied natural gas, that is, -164 °C or lower. When a steel material has poor low-temperature toughness, the safety as a structure for an extremely low-temperature storage tank may not be maintained. Thus, there is a growing demand for steel materials with improved low-temperature toughness that are applied to such a structure. In view of the demand, austenitic stainless steel which has an austenite microstructure exhibiting no brittleness at extremely low temperatures, 9 % Ni steel, or five thousand series aluminum alloys have been conventionally used. However, the alloy cost and manufacturing cost of those metal materials are high, and thus there is a demand for steel plates which are inexpensive and excellent in extremely low-temperature toughness. As new steel plates replacing conventional steel for extremely low temperatures, high-Mn steel added with a large amount of Mn which is a relatively inexpensive austenite-stabilizing element to form an austenite microstructure is considered to be used as a structural steel plate used in an extremely low-temperature environment.
- However, when a steel plate having an austenite microstructure is placed in a corrosive environment, austenite crystal grain boundaries are eroded by corrosion and when a tensile stress is added, stress corrosion cracking easily occurs, which is a problem of high-Mn steel. In manufacturing a structure for a storage tank of liquefied gas and the like, a steel substrate of a steel plate may be exposed, and when the exposed steel material surface contacts with water vapor containing corrosive substances including salinity, water, and oil, the steel material would be corroded. In the corrosion reaction on a steel plate surface, oxide (rust) is formed from iron by an anodic reaction. Meanwhile, hydrogen is generated by a cathodic reaction of water to enter into the steel, causing hydrogen embrittlement. When residual stress generated by bending or welding during manufacturing or load stress in an operating environment is exerted thereon, stress corrosion cracking may be caused, leading to rupture of a structure. Conventional high-Mn steel may be inferior in terms of corrosion resistance to not only austenitic stainless steel but also 9 % Ni steel and normal low-alloy steel. Therefore, from the viewpoint of safety, it is important that the steel material to be used has not only high strength and toughness at extremely low temperatures but also excellent corrosion resistance.
- For example,
JP 2015-508452 A -
JP 2016-84529 A -
JP 2016-196703 A
JP 2016 196703 A JP 2016 084529 A -
- PTL 1:
JP 2015-508452 A - PTL 2:
JP 2016-84529 A - PTL3:
JP 2016-196703 A - However, there is room for consideration in the steel materials described in PTL 1, PTL 2, and PTL 3 from the viewpoint of manufacturing cost for obtaining strength and low-temperature toughness and corrosion resistance when the austenite steel material is placed in a salinity corrosive environment.
- It could thus be helpful to provide high-Mn steel excellent in corrosion resistance, in particular corrosion resistance in a salinity corrosive environment.
- To achieve the aforementioned object, the inventors conducted extensive study on high-Mn steel as to various factors determining the chemical composition and manufacturing conditions to discover the following.
- a. In adding Cr to high-Mn steel, the addition amount of Cr and the amount of dissolved Cr is properly controlled to thereby make it possible to delay an initial corrosion reaction on a steel plate surface in a salinity corrosive environment. In this way, the hydrogen amount entering into steel can be reduced to suppress the stress corrosion cracking of austenite steel.
- b. Further, a measure of improving crystal grain boundary strength is valid for effectively suppressing rupture of austenite originating from crystal grain boundaries. In particular, P is an element which is easily segregated, as with Mn, during a solidification process of a slab and lowers the crystal grain boundary strength of a portion crossing such a segregation portion. Therefore, impurity elements such as P need to be reduced.
- This invention is based on the above discoveries and further investigation conducted by the inventors. The primary features of this invention are as specified in the appended claims.
- In this invention, "excellent in corrosion resistance" means a fracture stress of 400 MPa or more when a test in accordance with the Slow Strain Rate Test Method based on NACE Standard TM0111-2011 is performed by immersing in artificial seawater (chloride ion concentration of 18000 ppm) at 23 °C and performing a constant-rate tensile test at a strain rate of 4 × 10-7 inch/s.
- According to this invention, it is possible to provide a steel plate excellent in corrosion resistance, in particular, corrosion resistance in a salinity corrosive environment. Therefore, when our steel plate is used for a steel structure used in an extremely low-temperature environment such as a tank for a storage tank of liquefied gas, the safety and the service life of the steel structure is significantly improved, thus producing significantly advantageous effects in industrial terms. Further, our steel plate is inexpensive compared with conventional materials, and thus excellent in economic efficiency.
- Our steel plate will be described in detail hereinafter
- The chemical composition of our steel plate and the reasons for the limitations thereof are described first. In this invention, to ensure excellent corrosion resistance, the chemical composition of the steel plate is defined as follows. In the description of the chemical composition, "%" denotes "mass%" unless otherwise noted.
- C, which is effective for increasing strength and an inexpensive austenite-stabilizing element, is an important element to obtain austenite. To obtain this effect, the C content needs to be 0.20 % or more. On the other hand, a C content beyond 0.70 % promotes excessive precipitation of Cr carbides and Nb, V, and Ti based carbides, and thus lowers low-temperature toughness and becomes a corrosion origin. Therefore, the C content is set to be 0.20 % or more and 0.70 % or less, and preferably 0.25 % or more and 0.60 % or less.
- Si acts as a deoxidizer, is necessary for steelmaking, and is effective at increasing the strength of a steel plate by solid solution strengthening when dissolved in steel. To obtain such an effect, the Si content needs to be 0.05 % or more. On the other hand, a Si content beyond 1.00 % may deteriorate weldability and surface characteristics, lowering stress corrosion cracking resistance. Therefore, the Si content is set to 0.05 % or more and 1.00 % or less, and preferably 0.07 % or more and 0.50 % or less.
- Mn is a relatively inexpensive austenite-stabilizing element. In this invention, Mn is an important element for achieving both high strength and extremely low-temperature toughness. To obtain those effects, the Mn content needs to be 15.0 % or more. On the other hand, the Mn content beyond 35.0 % causes saturation of the effect of improving the extremely low-temperature toughness, increasing alloy costs. Further, such a high Mn content deteriorates weldability and cuttability, and further promotes segregation as well as the occurrence of stress corrosion cracking. Therefore, the Mn content is set to 15.0 % or more and 35.0 % or less, and preferably 18.0 % or more and 28.0 % or less.
- When the P content is beyond 0.030 %, P segregates to grain boundaries to lower grain boundary strength and becomes an origin of stress corrosion cracking. Therefore, the upper limit of the P content is 0.030 %, and desirably, the P content is kept as small as possible. Properties are improved as the P content is lower, and thus, the P content is preferably set to 0.024 % or less, and more preferably 0.020 % or less. On the other hand, reducing the P content to less than 0.001 % involves high steelmaking costs and impairs economic efficiency. Thus, the content of 0.001 % or more is allowable.
- S deteriorates the low-temperature toughness and ductility of the base metal. Therefore, the upper limit of the S content is 0.0200 %, and desirably, the S content is kept as small as possible. Therefore, the S content is set to 0.0200 % or less, and preferably 0.0180 % or less. On the other hand, reducing the S content to less than 0.0001 % involves high steelmaking costs and impairs economic efficiency. Thus, the content of 0.0001 % or more is allowable.
- Al acts as a deoxidizer and is used most commonly in molten steel deoxidizing processes to obtain a steel plate. Al also has an effect of fixing solute N in steel to form AlN, thus suppressing coarsening of crystal grains. Additionally, Al has an effect of suppressing deterioration of toughness caused by decrease in solute N. To obtain such an effect, the Al content needs to be 0.010 % or more. On the other hand, a Al content beyond 0.100 % may form coarse nitrides which would become an origin of corrosion and fracture, thus lowering stress corrosion cracking resistance. Further, Al diffuses to a weld metal portion during welding to deteriorate toughness of the weld metal. Thus, the Al content is set to 0.100 % or less, and preferably 0.020 % or more and 0.070 % or less.
- Cr is an important element because it is contained in a suitable amount to thereby produce an effect of delaying an initial corrosion reaction on a steel plate surface in a salinity corrosive environment to decrease the amount of hydrogen entering a steel plate and improve stress corrosion cracking resistance. When the Cr content is increased, corrosion resistance can be improved. On the other hand, Cr inevitably precipitates in the form of, for example, a nitride, a carbide, or a carbonitride during rolling and those precipitates may become an origin of corrosion and fracture to deteriorate stress corrosion cracking resistance. Therefore, the Cr content is set to 0.5 % or more and 8.0 % or less.
- Examining in detail the Cr effect which delays an initial corrosion reaction on a steel plate surface in a salinity corrosive environment, it has been found that the amount of solute Cr is important to ensure this effect, and when Cr exists in a solid solution state in an amount of 0.3 % or more, the effect is surely exhibited. On the other hand, it is necessary to devise manufacturing conditions to make Cr solid solution state and since the lower limit of Cr solid dissolution ratio which can be stably ensured by a minor change of manufacturing conditions is 60 %, the Cr content needs to be at least 0.5 % to obtain solute Cr in an amount of 0.3 % or more. The amount of solute Cr is preferably 1.0 % or more and 6.0 % or less, and more preferably 1.2 % or more and 5.5 % or less. The solid solution state refers to a state in which solute atoms exist as atoms without forming precipitates.
- N is an austenite-stabilizing element and an element which is effective for improving extremely low-temperature toughness. Further, N has an effect of bonding with Nb, V, and Ti to finely precipitate as nitrides or carbonitrides and serving as a diffusible hydrogen trapping site to suppress stress corrosion cracking. To obtain such an effect, the N content needs to be 0.0010 % or more. On the other hand, a N content beyond 0.0300 % promotes the formation of excessive nitrides or carbonitrides to reduce the solute element amount, lowering not only corrosion resistance but also toughness. Therefore, the N content is set to 0.0010 % or more and 0.0300 % or less, and preferably 0.0020 % or more and 0.0150 % or less.
- In this invention, to further improve corrosion resistance, in addition to the above essential elements, the following elements can be contained as necessary:
Nb: 0.003 % or more and 0.030 % or less and V: 0.01 % or more and 0.10 % or less, and Ti: 0.003 % or more and 0.040 % or less. - Nb precipitates as carbonitrides and the formed carbonitrides serve as a diffusible hydrogen trapping site. Thus, Nb is an element which has an effect of suppressing stress corrosion cracking. To obtain such an effect, Nb is preferably contained in an amount of 0.003 % or more. On the other hand, when the Nb content is more than 0.030 %, coarse carbonitrides may precipitate to become an origin of fracture. Further, the precipitates may be coarsened to deteriorate base metal toughness. Therefore, when Nb is contained, the Nb content is preferably set to 0.003 % or more and 0.030 % or less, more preferably 0.005 % or more and 0.025 % or less, and further preferably 0.007 % or more and 0.022 % or less.
- V precipitates as carbonitrides and the formed carbonitrides serve as a diffusible hydrogen trapping site. Thus, V is an element which has an effect of suppressing stress corrosion cracking. To obtain such an effect, V is preferably contained in an amount of 0.01 % or more. On the other hand, when the V content is more than 0.10 %, coarse carbonitrides may precipitate to become an origin of fracture. Further, the precipitates may be coarsened to deteriorate base metal toughness. Therefore, when V is contained, the V content is preferably set to 0.01 % or more and 0.10 % or less, more preferably 0.02 % or more and 0.09 % or less, and further preferably 0.03 % or more and 0.08 % or less.
- Ti precipitates as nitrides or carbonitrides and the formed nitrides or carbonitrides serve as a diffusible hydrogen trapping site. Thus, Ti is an element which has an effect of suppressing stress corrosion cracking. To obtain such an effect, Ti is preferably contained in an amount of 0.003 % or more. On the other hand, when the Ti content is more than 0.0040 %, the precipitates may be coarsened to deteriorate base metal toughness. Further, coarse carbonitrides may precipitate to become an origin of fracture. When Ti is contained, the Ti content is preferably set to 0.003 % or more and 0.040 % or less, more preferably 0.005 % or more and 0.035 % or less, and further preferably 0.007 % or more and 0.032 % or less.
- In this invention, to further improve corrosion resistance, the chemical composition may optionally contain at least one selected from the group of Cu: 0.01 % or more and 0.50 % or less, Ni: 0.01 % or more and 0.50 % or less, Sn: 0.01 % or more and 0.30 % or less, Sb: 0.01 % or more and 0.30 % or less, Mo: 0.01 % or more and 2.0 % or less, and W: 0.01 % or more and 2.0 % or less.
- Cu, Ni, Sn, Sb, Mo, and W are elements which are added with Cr to thereby improve corrosion resistance of high-Mn steel in a salinity corrosive environment. Cu, Sn, and Sb have an effect of increasing hydrogen overvoltage in a steel material to thereby suppress a hydrogen evolution reaction corresponding to the cathodic reaction. Ni forms a precipitation layer on a steel material surface and physically suppresses permeation of corrosive anions such as Cl- into a steel substrate. Further, Cu, Ni, Sn, Sb, Mo, and W are liberated as a metal ion from a steel material surface during corrosion and densify corrosion products, thereby suppressing permeation of corrosive anions into a steel interface (interface between a rust layer and a steel substrate). Mo and W are liberated as MO4 2- and WO4 2-, respectively, and adsorbed in the corrosive products or to the steel plate surface, thereby imparting cation selective permeability and electrically suppressing permeation of corrosive anions into the steel substrate.
- The above effects become apparent when those elements coexist with Cr in high-Mn steel and are exerted when those elements are contained in an amount not lower than the respective lower limits listed above. However, large contents of those elements deteriorate weldability and toughness and are disadvantageous in terms of costs.
- Therefore, preferred contents are: a Cu content of 0.01 % or more and 0.50 % or less; a Ni content of 0.01 % or more and 0.50 % and less; a Sn content of 0.01 % or more and 0.30 % or less; a Sb content of 0.01 % or more and 0.30 % or less; a Mo content of 0.01 % or more and 2.0 % or less; and a W content of 0.01 % or more and 2.0 % or less.
- More preferred contents are: a Cu content of 0.02 % or more and 0.40 % or less; a Ni content of 0.02 % or more and 0.40 % or less; a Sn content of 0.02 % or more and 0.25 % or less; a Sb content of 0.02 % or more and 0.25 % or less; a Mo content of 0.02 % or more and 1.9 % or less; and a W content of 0.02 % or more and 1.9 % or less.
- Similarly, in this invention, to further improve corrosion resistance, the chemical composition may optionally contain at least one selected from the group of Ca: 0.0005 % or more and 0.0050 % or less, Mg: 0.0005 % or more and 0.0100 % or less, and REM: 0.0010 % or more and 0.0200 % or less.
- Ca, Mg, and REM are elements useful for morphological control of inclusions and can be contained as necessary. As used herein, the morphological control of inclusions means granulating elongated sulfide-based inclusions. The morphological control of inclusions improves ductility, toughness, and sulfide stress corrosion cracking resistance. To obtain such effects, Ca and Mg are preferably contained in an amount of 0.0005 % or more and REM is preferably contained in an amount of 0.0010 % or more. On the other hand, when these elements are contained in a large amount, not only the amount of nonmetallic inclusions may be increased, ending up deteriorating ductility, toughness, and sulfide stress corrosion cracking resistance, but also an economic disadvantage may be entailed.
- Therefore, when Ca is contained, the Ca content is preferably set to 0.0005 % or more and 0.0050 % or less, when Mg is contained, the Mg content is preferably set to 0.0005 % or more and 0.0100 % or less, and when REM is contained, the REM content is preferably set to 0.0010 % or more and 0.0200 % or less. A Ca content of 0.0010 % or more and 0.0040 % or less, a Mg content of 0.0010 % or more and 0.0040 % or less, and a REM content is 0.0020 % or more and 0.0150 % or less are more preferable.
- The following describes manufacturing conditions in this invention. In the following description, temperatures (°C) refer to the temperature of the mid-thickness part of a steel plate.
[Reheating temperature of a steel raw material: 1000 °C or higher and 1300 °C or lower] - Heating a steel raw material to 1000 °C or higher is for dissolving carbonitrides in the microstructure to make the crystal grain size and the like uniform. Specifically, when the heating temperature is lower than 1000 °C, carbonitrides are not sufficiently dissolved and thus desired properties cannot be obtained. Further, heating at a temperature higher than 1300 °C deteriorates material properties due to coarsening of crystal grain size and needs excessive energy, lowering productivity. Thus, the upper limit of the heating temperature is set to 1300 °C, preferably 1050 °C or higher and 1250 °C or lower, and more preferably 1070 °C or higher and 1250 °C or lower.
- Since in hot rolling with a rolling reduction ratio of less than 3, an effect of promoting recrystallization and homogenizing a grain size cannot be obtained, coarse austenite grains remain and a part having the coarse austenite grains is preferentially oxidized, thereby deteriorating corrosion resistance. Therefore, the rolling reduction ratio in hot rolling is limited to 3 or more. On the other hand, the upper limit of the rolling reduction ratio needs to be 30 for the reasons given below. As used herein, the rolling reduction ratio is defined by a plate thickness of a material to be rolled / a plate thickness of a steel plate after hot rolling.
- When the finish rolling temperature is lower than 750 °C, the amount of carbide precipitates during rolling is significantly increased, and even when the time for which a material to be rolled resides within a temperature range of 600 °C to 950 °C is 30 minutes or less, a sufficient amount of solute Cr may not be obtained, lowering corrosion resistance. Further, when rolling is performed at a temperature of lower than 750 °C, deformation resistance is increased to apply an excessive load to a manufacturing apparatus. Thus, the finish rolling temperature is set to 750 °C or higher. From the viewpoint of suppressing significant coarsening of crystal grain size, the upper limit of the finish rolling temperature is preferably 1050 °C or lower.
- In hot rolling, if the time for which a material to be rolled resides within a temperature range of 600 °C to 950 °C (residence time) is more than 30 minutes, a large amount of carbonitrides and carbides precipitate during rolling and the necessary amount of solute Cr cannot be obtained, lowering corrosion resistance and extremely-low temperature toughness. Therefore, the time for which a material to be rolled resides within a temperature range of 600 °C to 950 °C is limited to 30 minutes or less. The time for which a material to be rolled resides within a temperature range of 600 °C to 950 °C is preferable as short as possible, and thus, no lower limit is placed thereon.
- To set the time for which a material to be rolled resides within a temperature range of 600 °C to 950 °C to 30 minutes or less, the length of the material to be rolled is made to be 5000 mm or less and the rolling reduction ratio of the material to be rolled is limited to 30 or less as described above. This is because when the length of the material to be rolled is more than 5000 mm or the rolling reduction ratio is more than 30, the rolling time becomes long and as a result, the time for which a material to be rolled resides within a temperature range of 600 °C to 950 °C exceeds 30 minutes.
- Since when the average cooling rate within a temperature range of 600 °C to 700 °C is less than 3 °C/s, a large amount of precipitates such as Cr carbides are formed, the average cooling rate is limited to 3 °C/s or more. The average cooling rate is preferable as fast as possible, and thus, no upper limit is placed thereon.
- Steels of Nos. 1 to 28 listed in Table 1 were produced by steelmaking to obtain slabs, subsequently the slabs were formed into steel plates of sample Nos. 1 to 34 having a plate thickness of 6 mm to 50 mm under the manufacturing conditions listed in Table 2, and the steel plates were subjected to the following test.
- The corrosion resistance test was performed in accordance with the Slow Strain Rate Test Method based on NACE Standard TM0111-2011 (hereinafter, referred to as "SSRT test"). Test pieces having a shape of notched Type A round bar were used. The test pieces were immersed in artificial seawater (having chloride ion concentration of 18000 ppm) at 23 °C and subjected to a constant-rate tensile test at a strain rate of 4 × 10-7 inch/s. In this invention, a test piece having a fracture stress of 400 MPa or more was considered as having excellent stress corrosion cracking resistance. The results thus obtained are listed in Table 2.
Table 2 Sample No. Material No. Material length (mm) Manufacturing conditions Base metal properties Stress corrosion cracking resistance Remarks Product thickness (mm) Heating temperature (°C) Rolling reduction ratio Finish rolling temperature (°C) Cooling start (°C) Cooling stop (°C) Average cooling rate* 1 (°C/s) Residence time (min) Solute Cr ratio (%) Fracture stress (MPa) 1 1 4500 30 1100 5 850 800 500 30 10 85 559 Inventive Example 2 2 5000 50 1200 3 900 850 550 15 5 95 529 3 3 1200 6 1200 30 760 700 550 130 25 75 518 4 4 4000 30 1150 7 850 800 500 40 15 80 573 5 5 2000 12 1200 15 850 750 500 75 20 90 580 6 6 4000 30 1250 6 850 800 600 30 10 75 554 7 7 3000 12 1150 10 850 780 550 70 20 85 569 9 9 1800 12 1200 15 900 750 550 30 30 70 502 8 8 5000 50 1200 4 900 800 550 15 8 90 581 10 10 5000 50 1280 3 900 750 550 10 5 75 503 11 11 4000 30 1150 5 800 750 500 30 8 85 495 12 12 2000 12 1050 15 750 700 500 70 15 80 481 13 13 2500 12 1150 10 800 750 600 75 10 85 590 14 14 1200 6 1250 25 750 700 450 140 30 65 483 15 15 1500 6 1150 20 750 700 400 140 30 70 521 16 16 5000 50 1200 4 950 900 550 15 5 90 546 17 17 2500 12 1150 10 800 750 500 75 15 80 536 18 18 1000 6 1050 30 800 700 500 70 30 60 335 Comparative Example 19 19 2000 12 1050 15 750 700 500 70 *2 *2 *2 20 20 5000 50 1280 4 850 800 600 10 15 90 380 21 21 2000 12 1100 15 800 750 550 65 *2 *2 *2 22 22 3000 30 1200 5 850 800 550 30 20 85 351 23 23 1000 6 1100 30 750 700 450 70 30 60 305 24 24 2000 12 1050 15 800 750 500 70 20 85 378 25 25 1200 6 1150 30 900 850 550 35 30 60 352 26 26 1000 6 1200 30 800 700 500 130 25 65 358 27 27 2000 12 1100 15 800 750 550 30 25 50 329 28 28 2000 12 1150 15 750 700 500 35 20 70 345 29 9 4000 30 975 6 850 800 600 35 10 45 303 30 9 2000 12 1200 15 600 500 400 - 30 50 294 31 9 2000 6 1200 30 800 naturally cooled naturally cooled 2 50 40 285 32 9 2000 6 1100 40 800 750 500 5 40 40 292 33 9 5000 50 1200 3 850 800 600 15 45 45 292 34 9 5500 30 1200 7 850 800 600 30 40 45 322 Note: Underlines represent out of the scope of this invention. * 1 indicates an average cooling rate within a temperature range of700 °C to 600 °C.
*2 Measurement was omitted because an austenite microstructure was not obtained. - Examples (sample Nos. 1 to 17) according to this invention were confirmed to have corrosion resistance satisfying 400 MPa or more for the fracture stress of the SSRT test. In contrast, comparative examples (sample Nos. 18 to 34) outside the scope of this disclosure did not satisfy the above-described target performance in terms of stress corrosion cracking resistance.
Claims (2)
- A steel plate comprising a chemical composition containing, in mass%,C: 0.20 % or more and 0.70 % or less,Si: 0.05 % or more and 1.00 % or less,Mn: 15.0 % or more and 35.0 % or less,P: 0.030 % or less,S: 0.0200 % or less,Al: 0.010 % or more and 0.100 % or less,Cr: 0.5 % or more and 8.0 % or less, andN: 0.0010 % or more and 0.0300 % or less,optionally, in mass%, at least one selected from the group consisting ofNb: 0.003 % or more and 0.030 % or less,V: 0.01 % or more and 0.10 % or less,Ti: 0.003 % or more and 0.040 % or less,Cu: 0.01 % or more and 0.50 % or less,Ni: 0.01 % or more and 0.50 % or less,Sn: 0.01 % or more and 0.30 % or less,Sb: 0.01 % or more and 0.30 % or less,Mo: 0.01 % or more and 2.0 % or less,W: 0.01 % or more and 2.0 % or less,Ca: 0.0005 % or more and 0.0050 % or less,Mg: 0.0005 % or more and 0.0100 % or less, andREM: 0.0010 % or more and 0.0200 % or less, with the balance being Fe and inevitable impurities,wherein at least 60 % of the contained Cr is solute Cr.
- A method for manufacturing a steel plate, comprising:heating a steel raw material having the chemical composition according to claim 1 to 1000 °C or higher and 1300 °C or lower; subsequently hot rolling the steel raw material with a rolling reduction ratio of 3 or more and 30 or less, a finish rolling temperature of 750 °C or higher, and a time for which a material to be rolled resides within a temperature range of 600 °C to 950 °C of 30 minutes or less to obtain a hot-rolled steel plate; and then, cooling the hot-rolled steel plate at an average cooling rate of 3 °C/s or more within a temperature range of 600 °C to 700 °C,wherein the length of the material to be rolled is made to be 5000 mm or less.
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JP4529872B2 (en) * | 2005-11-04 | 2010-08-25 | 住友金属工業株式会社 | High Mn steel material and manufacturing method thereof |
JP5041029B2 (en) * | 2010-04-30 | 2012-10-03 | 住友金属工業株式会社 | Method for producing high manganese steel |
CN104220617B (en) | 2011-12-27 | 2016-10-26 | Posco公司 | There is the machining property of excellence and there is in welding heat affected region the austenitic steel of low-temperature flexibility, and manufacture method |
JP6645103B2 (en) * | 2014-10-22 | 2020-02-12 | 日本製鉄株式会社 | High Mn steel material and method for producing the same |
JP6693217B2 (en) * | 2015-04-02 | 2020-05-13 | 日本製鉄株式会社 | High Mn steel for cryogenic temperatures |
JP6589535B2 (en) * | 2015-10-06 | 2019-10-16 | 日本製鉄株式会社 | Low temperature thick steel plate and method for producing the same |
KR101758525B1 (en) * | 2015-12-23 | 2017-07-27 | 주식회사 포스코 | HEAT TREATMENT METHOD OF HIGH STRENGH AND HIGH ELONGATION HIGH-Mn STEEL |
JP6728779B2 (en) * | 2016-03-03 | 2020-07-22 | 日本製鉄株式会社 | Low temperature thick steel plate and method of manufacturing the same |
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2018
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EP2971211B1 (en) * | 2013-03-15 | 2020-04-15 | ExxonMobil Research and Engineering Company | Methods of making enhanced wear resistant steel |
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SG11202002379QA (en) | 2020-04-29 |
WO2019059095A1 (en) | 2019-03-28 |
EP3686306A4 (en) | 2020-07-29 |
KR102363482B1 (en) | 2022-02-15 |
JP6760476B2 (en) | 2020-09-23 |
MY193070A (en) | 2022-09-26 |
EP3686306A1 (en) | 2020-07-29 |
KR20200041938A (en) | 2020-04-22 |
CN111108225B (en) | 2021-09-24 |
PH12020550108A1 (en) | 2020-12-07 |
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JPWO2019059095A1 (en) | 2019-11-14 |
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