EP3561115A1 - Thick steel plate having excellent low-temperature impact toughness and ctod characteristic and manufacturing method therefor - Google Patents

Thick steel plate having excellent low-temperature impact toughness and ctod characteristic and manufacturing method therefor Download PDF

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EP3561115A1
EP3561115A1 EP17885144.0A EP17885144A EP3561115A1 EP 3561115 A1 EP3561115 A1 EP 3561115A1 EP 17885144 A EP17885144 A EP 17885144A EP 3561115 A1 EP3561115 A1 EP 3561115A1
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Prior art keywords
steel sheet
thick steel
impact toughness
equation
ctod
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EP17885144.0A
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German (de)
French (fr)
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EP3561115A4 (en
EP3561115B1 (en
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Woo-Gyeom KIM
Kyung-Keun Um
Ki-Hyun Bang
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Posco Holdings Inc
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Posco Co Ltd
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    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/001Heat treatment of ferrous alloys containing Ni
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/005Heat treatment of ferrous alloys containing Mn
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    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/008Heat treatment of ferrous alloys containing Si
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    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
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    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/021Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving particular fabrication steps or treatments of ingots or slabs
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226Hot rolling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0263Modifying the physical properties of ferrous metals or ferrous alloys 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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    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/002Ferrous 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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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/08Ferrous alloys, e.g. steel alloys containing nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/12Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/14Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/16Ferrous alloys, e.g. steel alloys containing copper
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/001Austenite
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/005Ferrite
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/008Martensite

Definitions

  • the present disclosure relates to a thick steel sheet having excellent low temperature impact toughness and CTOD properties which may be preferably applied to an offshore structural steel material, and a method of manufacturing the same.
  • the North Pole has been considered as a land storing future energy sources, and the development of petroleum and gas sources have been conducted, centering on countries neighboring the Arctic Circle.
  • the development of energy sources in the Arctic will be accelerated due to the exhaustion of energy source of land, offshore regions, and deep sea regions.
  • a steel material applied to offshore structure facilities for mining, drilling, storing energy sources developed in the polar regions may need to have toughness at a low temperature of -60°C or lower, and may need to have a CTOD value representing fatigue fracture properties at -60°C. Also, strength and thickness of a steel material have been increased as the sizes of facilities have increased and facilities have been integrated.
  • brittleness cracks As for resistance against brittleness fracture, generally, there may be resistance against the formation of brittleness cracks and resistance against the propagation of brittleness cracks.
  • the formation of brittleness cracks may refer to, after fatigue cracks started in a defect portion in a structure is grown to a certain size, the generation of brittleness cracks from the grown fatigue cracks when high external stress is applied.
  • the resistance properties of the material which may prevent the formation of brittleness cracks may be referred to as resistance against the formation of brittleness cracks, and the resistance is tested using a CTOD (crack tip opening displacement) testing method prescribed in BS 7448 standard or ASTM 1290 standard.
  • CTOD crack tip opening displacement
  • reference 1 discloses a method of manufacturing a steel sheet to maintain excellent CTOD properties by maintaining a certain level of reduction ratios of final three passes during rolling the steel sheet including a rolling process in which a reduction ratio is low, such as a width widening rolling.
  • reference 1 has a problem in which it may be difficult to sufficient low temperature toughness and CTOD properties.
  • An aspect of the present disclosure is to provide a thick steel sheet having excellent low temperature impact toughness and CTOD properties which may be preferably applied to an offshore structural steel material, and a method of manufacturing the same.
  • An aspect of the present disclosure relates to a thick steel sheet having excellent low temperature impact toughness and CTOD properties comprising, by weight%, 0.02 to 0.06% of C, 0.005 to 0.08% of Si, 1.0 to 2.0% of Mn, 0.01% or less of P, 0.003% or less of S, 0.001 to 0.01% of Al, 0.5 to 2.0% of Ni, 0.001 to 0.02% of Ti, 0.005 to 0.03% of Nb, 0.05 to 0.4% of Cu, 0.002 to 0.006% of N, and a balance of Fe and inevitable impurities, the thick steel sheet satisfies Equation 1 and Equation 2 below, and a microstructure comprises ferrite of 95 area% or higher, and a sum of MA and cementite of 2 area% or lower.
  • An aspect of the present disclosure relates to a method of manufacturing a thick steel sheet having excellent low temperature impact toughness and CTOD properties, the method comprising heating a slab at 1020 to 1150°C, the slab comprising, by weight%, 0.02 to 0.06% of C, 0.005 to 0.08% of Si, 1.0 to 2.0% of Mn, 0.01% or less of P, 0.003% or less of S, 0.001 to 0.01% of Al, 0.5 to 2.0% of Ni, 0.001 to 0.02% of Ti, 0.005 to 0.03% of Nb, 0.05 to 0.4% of Cu, 0.002 to 0.006% of N, and a balance of Fe and inevitable impurities, and satisfying Equation 1 and Equation 2 below; recrystallization-region rolling the heated slab at 900°C or higher; obtaining a thick steel sheet by performing a non-recrystallization-region rolling process for a finish rolling temperature to be Ar3 to 850°C after the recrystallization-region rolling; cooling the thickness steel sheet to 250°
  • excellent yield strength may be secured with respect to a thick steel sheet having a thickness of 50mm or greater, excellent impact toughness may be secured even at an extremely low temperature of about -80°C, and a thick steel sheet having impact toughness and CTOD properties at -60°C and a method of manufacturing the same may be provided, which are effects of the present disclosure.
  • a thick steel sheet having excellent low temperature impact toughness and CTOD properties may include, by weight%, 0.02 to 0.06% of C, 0.005 to 0.08% of Si, 1.0 to 2.0% of Mn, 0.01% or less of P, 0.003% or less of S, 0.001 to 0.01% of Al, 0.5 to 2.0% of Ni, 0.001 to 0.02% of Ti, 0.005 to 0.03% of Nb, 0.05 to 0.4% of Cu, 0.002 to 0.006% of N, and a balance of Fe and inevitable impurities, and may satisfy Equation 1 and Equation 2 below, and a microstructure may include ferrite of 95 area% or higher, and a sum of MA and cementite of 2 area% or lower. 3.0 ⁇ Mn + 2 ⁇ Ni ⁇ 4.3 0.05 ⁇ C + Si + 10 ⁇ Al ⁇ 0.25 (in Equation 1 and Equation 2, each element symbol indicates a content of each element by weight%).
  • a unit of a content of each element may be wt% unless otherwise indicated.
  • C is an element which may be effective for strengthening solid solution, and may improve strength by forming Nb, and the like, and carbide.
  • a content of C When a content of C is lower than 0.02%, the above-described effect may be insufficient. When a content of C exceeds 0.06%, the formation of MA may be facilitated, and pearlite may be formed such that impact and fatigue properties at a low temperature may be deteriorated. Thus, a preferable content of C may be 0.02 to 0.06%.
  • a more preferable lower limit content of C may be 0.025%, and an even more preferable lower limit content of C may be 0.03%.
  • a more preferable upper limit content of C may be 0.055%, and an even more preferable upper limit content of C may be 0.05%.
  • Si is an element which may deoxidize molten steel auxiliary to Al, and may help improving yield strength and tensile strength, but may adversely affect impact and fatigue properties at a low temperature.
  • Si When a content of Si exceeds 0.08%, Si may interfere with dispersion of C such that the formation of MA may be facilitated, which may adversely affect impact and fatigue properties at a low temperature. Also, to control a content of Si to be 0.005% or less, a processing time of a steel making process may greatly increase, such that productivity may decrease. Thus, a preferable content of Si may be 0.005 to 0.08%.
  • a more preferable lower limit content of Si may be 0.01%, a more preferable upper limit content of Si may be 0.07%, and an even more preferable upper limit content of Si may be 0.055%.
  • Mn may have a great effect in increasing strength by strengthening solid solution, and thus, 1.0% or higher of Mn may be added.
  • a content of Mn is excessive, toughness may degrade due to the formation of an MnS inclusion, and the segregation of a central portion.
  • a preferable upper limit content of Mn may be 2.0%.
  • P is an element which may cause grain boundary segregation, and may thus be a cause of weakening steel.
  • a content of P may need to be controlled to be low as possible as P is one of impurities, and it may be preferable to control a content of P to be 0.01% or less. It may be substantially impossible to control a content of P to be 0%, and thus, 0% may not be included.
  • S may be a factor which may form an MnS inclusion by being combined with Mn, and the MnS inclusions may degrade low temperature toughness.
  • a content of S may need to be controlled to be low as possible as S is one of impurities. It may be preferable to control a content of S to be 0.003% or less to secure low temperature toughness and low temperature fatigue properties. It may be substantially impossible to control a content of S to be 0%, and thus, 0% may not be included.
  • Al is a main deoxidizer in the present disclosure, and it may be required to add 0.001% or higher of Al.
  • a content of Al exceeds 0.01%, Al may be a cause of gradation of low temperature toughness due to an increase of a fraction and a size of Al 2 O 3 inclusion.
  • Al similarly to Si, Al may facilitate the formation of an MA phase in a base material and a welding heat affected portion such that low temperature toughness and low temperature fatigue properties may degrade.
  • a preferable content of Al may be 0.001 to 0.01%.
  • Ni may not greatly improve strength, but Ni may improve strength and toughness at the same time.
  • Ni When a content of Ni is lower than 0.5%, the above-described effect may be insufficient. When a content of Ni exceeds 2.0%, Ni may facilitate the formation of MA due to an increase of hardenability such that impact and CTOD toughness may be deteriorated.
  • Ti is an element which may form a precipitation by being combined with oxygen or nitrogen, and may accordingly prevent a structure from being coarse, and may contribute to refinement and improvement of toughness.
  • Nb is an element which may prevent recrystallization during rolling or cooling by precipitating solute or carbonitride and may thus refine a structure and may increase strength.
  • Cu is an element which may not greatly degrade impact properties, and may improve strength by solid solution and precipitation.
  • N is an element which may refine an austenite structure during reheating by forming a precipitation along with Ti, Nb, Al, and the like, and may thus be helpful for improving strength and toughness. It may be preferable to add 0.002% or higher of N.
  • a content of N exceeds 0.006%, surface cracks may be created at a high temperature, and residual N which remains after a precipitation is formed may be present in an atomic state and may decrease toughness.
  • a preferable content of N may be 0.002 to 0.006%.
  • a remainder other than the above-described composition is Fe.
  • inevitable impurities may be inevitably added from raw materials or a surrounding environment, and thus, impurities may not be excluded.
  • a person skilled in the art may be aware of the impurities, and thus, the descriptions of the impurities may not be provided in the present disclosure.
  • An alloy composition of the present disclosure may need to satisfy the above-described element contents, and may also satisfy Equation 1 and Equation 2 below. 3.0 ⁇ Mn + 2 ⁇ Ni ⁇ 4.3 0.05 ⁇ C + Si + 10 ⁇ Al ⁇ 0.25 (in Equation 1 and Equation 2, each element symbol indicates a content of each element by weight%).
  • Equation 1 and Equation 2 may be to secure excellent low temperature impact toughness and CTOD properties without degradation of strength, and may be designed in consideration of correlation affecting an MA preventing effect and strength.
  • contents of C, Si, and Al may be controlled, and to compensate for degradation of strength caused by the control of contents of the elements, Mn and Ni may need to be added in accordance with Equation 1.
  • Equation 1 When a value of Equation 1 is lower than 3.0, an effect of improving strength may be insufficient. When the value exceeds 4.3, low temperature impact toughness and CTOD properties may degrade.
  • a preferable value of Equation 2 may be 0.05 or higher for steel making processes such as deoxidation, and the like.
  • a value of Equation 2 is lower than 0.05, it may be difficult to secure strength.
  • the value exceeds 0.25 a large amount of MA phase may be formed such that low temperature impact toughness and CTOD properties may degrade.
  • the alloy composition of the present disclosure may further include one or more of 0.001 to 0.05% of Mo and 0.0002 to 0.005% of Ca by weight%.
  • Mo is an element which may be effective for improving strength by increasing hardenability.
  • a preferable content of Mo may be 0.001% or higher.
  • toughness may degrade due to an increase of hardenability, and toughness may degrade by the formation of a precipitation of molybdenum carbide.
  • the Al-deoxidized Ca may be combined with S, mainly present as MnS, such that the formation of MnS may be prevented, and spheroidal CaS may be formed such that there may be an effect of preventing cracks in a central portion of a steel material.
  • S mainly present as MnS
  • spheroidal CaS may be formed such that there may be an effect of preventing cracks in a central portion of a steel material.
  • a content of Ca exceeds 0.005%, residual Ca may be combined with O and a coarse oxidated inclusion may be formed, which may work as a crack initiation point at a low temperature due to elongation and breakage of the inclusion during a rolling process.
  • a microstructure of a thick steel sheet of the present disclosure will be described in detail.
  • a microstructure of the thick steel sheet may include ferrite of 95 area% or higher, and a sum of MA and cementite of 2 area% or lower.
  • a structure of a base material and a fraction of MA may be important.
  • hardenability may increase, and C may be transformed to martensite having high hardenability or may remain as austenite, which may be referred to as martensite-austenite (MA).
  • MA may be vulnerable to fracture due to properties of high hardness, and may cause stress to be concentrated when soft ferrite around MA is transformed, and may accordingly work as initiation of fracture.
  • cementite may have a characteristic similar to that of MA, and may be a hard phase having hardenability higher than that of base material acicular ferrite, and cementite may deteriorate low temperature impact toughness and CTOD properties.
  • a sum of MA and cementite may be 2 area% or lower.
  • Ferrite has a grain size of 20 ⁇ m or less measured in equivalent circle diameter.
  • the grain size exceeds 20 ⁇ m, dislocation in ferrite may increase such that fracture propagation may easily occur such that low temperature impact toughness and CTOD properties may be deteriorated.
  • the smaller the grain size it may be more advantageous to securing low temperature impact toughness and CTOD properties, and thus, a lower limit content of ferrite may not be particularly limited.
  • Ferrite may also include polygonal ferrite and acicular ferrite, and specific fractions thereof may not be limited.
  • the thick steel sheet may have yield strength of 420MPa or higher, impact toughness of 200J or higher at -80°C, and a CTOD of 0.5mm or higher at -60°C. By securing such properties, the thick steel sheet may be appropriately applied to an offshore structural steel material used in an extremely low temperature environment. More preferably, a CTOD may be 1.0mm or higher at -60°C.
  • the thick steel sheet may have tensile strength of 500MPa or higher, an elongation rate of 25% or higher, and impact toughness of 400J or higher at -60°C.
  • the thickness steel sheet may have a thickness of 50 to 100mm.
  • the method of manufacturing a thick steel sheet having excellent low temperature impact toughness and CTOD properties may include heating a slab comprising the above-described alloy composition at 1020 to 1150°C; recrystallization-region rolling the heated slab at 900°C or higher; obtaining a thick steel sheet by performing a non-recrystallization-region rolling process for a finish rolling temperature to be Ar3 to 850°C after the recrystallization-region rolling; cooling the thickness steel sheet to 250°C or lower at a cooling speed of 2 to 15°C/sec; and tempering the cooled thick steel sheet at 500 to 650°C.
  • the slab satisfying the above-described alloy composition may be heated at 1020 to 1150°C.
  • the heated slab may be recrystallization-region rolled at 900°C or higher. When the temperature is lower than 900°C, it may be difficult to implement sufficient recrystallization of austenite.
  • the recrystallization-region rolling is performed at each of the reduction ratios of the final two passes to be within 15 to 20%, which may be to secure a uniform and fine final microstructure.
  • a thick steel sheet may be obtained by performing a non-recrystallization-region rolling for a finish rolling temperature to be Ar3 to 850°C after the recrystallization-region rolling.
  • a temperature of a surface of the thick steel sheet may be that of a two-phase region, and a two phase structure may be formed at a thickness of surface to 1/4t such that impact toughness may be deteriorated.
  • the finish rolling temperature exceeds 850°C, grain refinement may be insufficient such that strength and toughness may be deteriorated.
  • the non-recrystallization-region rolling may be performed for a thickness of the thick steel sheet to be 50 to 100mm.
  • the thick steel sheet may be cooled to 250°C or lower at a cooling speed of 2 to 15°C/sec.
  • cooling speed exceeds 15°C/sec, there may be a difference in properties due to a difference in cooling speed between a surface and a central portion of the thick steel sheet.
  • cooling speed is lower than 2°C/sec, distribution of acicular ferrite may decrease, and distribution of polygonal ferrite may increase.
  • the cooled thick steel sheet may be tempered at 500 to 650°C. Dislocation in an MA phase and ferrite may be factors which may greatly affect low temperature impact toughness and CTOD properties. Thus, the tempering may be performed to dissolve an MA phase and to decrease dislocation in ferrite.
  • the tempering temperature is lower than 500°C, the above-described effect may be insufficient.
  • carbide may be formed, which may degrade toughness.
  • Molten steel having a composition indicated in Table 1 below was prepared, and a slab was manufactured using a continuous casting process.
  • the slab was heated, recrystallization-region rolled, non-recrystallization-region roll, and cooled and tempered under manufacturing conditions as in Table 2 below, and a thick steel sheet having a thickness of 80mm was manufactured.
  • the recrystallization-region rolling was performed for each of reduction ratios of final two passes to be 18%.
  • a microstructure, mechanical properties, low temperature impact toughness and CTOD properties of the thick steel sheet were measured and listed in Table 3 below.
  • the microstructure was observed using a scanning electron microscope (SEM) and a transmission electron microscope (TEM), and a sum (a secondary phase) of MA and cementite was analyzed and listed in Table 3.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • a portion other than the secondary phase was ferrite including polygonal ferrite and acicular ferrite.
  • Yield strength, tensile strength, and an elongation rate were measured through a tensile test.
  • Low temperature impact toughness was measured through a charpy impact test at -80°C and -60°C.
  • CTOD properties a sample was processed to have a size of 60mm ⁇ 120mm ⁇ 300mm in perpendicular to a rolling direction in accordance with BS 7448 standards, fatigue cracks were inserted such that a fatigue crack length became 50% of a sample width, and a CTOD test was carried out at -60°C.
  • the CTOD test was performed three times for each steel sheet, and a minimum value among the test values obtained from the three times of tests was listed in Table 3.
  • Equation 1 is a value of Mn+2Ni
  • Equation 2 is value of C+Si+10Al
  • each element symbol indicates a content of each element by weight %.
  • Equation 2 Classification Steel Type Slab Heating Temperature (°C) Recrystal lization-Region rolling Terminating Temperature (°C) Non-Recryst allization-Region Rolling Terminating Temperature (°C) Cooling Terminating Temperature (°C) Cooling Speed (°C/s) Tempering Temperature (°C)
  • Inventive example 1 A 1105 1021 775 224 3.4 552
  • Inventive example 4 D 1110 1023 781 213 2.6 550
  • Comparative example 1 A 1121 1022 875 229 3.1 551 Comparative example 2 B 1105 1032 780 195 3.0 Not Conducted Comparative example 3 C
  • Inventive examples which satisfied the overall alloy composition and the manufacturing conditions suggested in the present disclosure secured yield strength of 420MPa or higher, impact toughness of 200J or higher at -80°C, and a CTOD value of 0.5mm or higher at -60°C, which indicate that low temperature impact toughness and CTOD properties were excellent.
  • FIG. 1 is an image of a microstructure of inventive example 1. A small amount of MA and cementite were formed, and a grain size was also fine.
  • Comparative examples 1 to 3 satisfied the alloy composition suggested in the present disclosure, but did not satisfy the manufacturing conditions.
  • Comparative examples 4 to 7 satisfied the manufacturing conditions suggested in the present disclosure, but did not satisfy the alloy composition.
  • FIG. 2 is graphs illustrating yield strength in accordance with an Mn+2Ni value and a CTOD value at -60°C.
  • Mn+2Ni value is lower than 3.0, strength decreased.
  • CTOD value at -60°C greatly decreased.

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Abstract

An aspect of the present invention relates to a thick steel plate having excellent low-temperature impact toughness and CTOD characteristics, the thick steel plate comprising, by weight %: 0.02-0.06% of C, 0.005-0.08% of Si, 1.0-2.0% of Mn, 0.01% or less of P, 0.003% or less of S, 0.001-0.01% of Al, 0.5-2.0% of Ni, 0.001-0.02% of Ti, 0.005-0.03% of Nb, 0.05-0.4% of Cu, 0.002-0.006% of N, and a balance of Fe and inevitable impurities with the proviso of satisfying the following equations, wherein the thick steel plate has a microstructure including ferrite in an amount of 95 area % or greater and a sum of MA and cementite in an amount of 2 area % or less : Equation 1: 3.0≤Mn+2Ni≤4.3 and Equation 2: 0.05≤C+Si+10Al≤0.25 (wherein element symbols each represent contents thereof by weight %) .

Description

    [Technical Field]
  • The present disclosure relates to a thick steel sheet having excellent low temperature impact toughness and CTOD properties which may be preferably applied to an offshore structural steel material, and a method of manufacturing the same.
  • [Background Art]
  • The North Pole has been considered as a land storing future energy sources, and the development of petroleum and gas sources have been conducted, centering on countries neighboring the Arctic Circle. The development of energy sources in the Arctic will be accelerated due to the exhaustion of energy source of land, offshore regions, and deep sea regions.
  • A steel material applied to offshore structure facilities for mining, drilling, storing energy sources developed in the polar regions may need to have toughness at a low temperature of -60°C or lower, and may need to have a CTOD value representing fatigue fracture properties at -60°C. Also, strength and thickness of a steel material have been increased as the sizes of facilities have increased and facilities have been integrated.
  • As for resistance against brittleness fracture, generally, there may be resistance against the formation of brittleness cracks and resistance against the propagation of brittleness cracks. The formation of brittleness cracks may refer to, after fatigue cracks started in a defect portion in a structure is grown to a certain size, the generation of brittleness cracks from the grown fatigue cracks when high external stress is applied. The resistance properties of the material which may prevent the formation of brittleness cracks may be referred to as resistance against the formation of brittleness cracks, and the resistance is tested using a CTOD (crack tip opening displacement) testing method prescribed in BS 7448 standard or ASTM 1290 standard. Thus, excellent CTOD properties may indicate that resistance against the formation of brittleness cracks may be excellent.
  • A large amount of research and development have been conducted to secure low temperature impact toughness and CTOD properties. For example, reference 1 discloses a method of manufacturing a steel sheet to maintain excellent CTOD properties by maintaining a certain level of reduction ratios of final three passes during rolling the steel sheet including a rolling process in which a reduction ratio is low, such as a width widening rolling.
  • However, reference 1 has a problem in which it may be difficult to sufficient low temperature toughness and CTOD properties.
  • Also, as the use environments have become harsh, there has been demand for development of a technique which may secure excellent impact toughness even at an extremely low temperature of about -80°C, and there has been demand for development of a thick steel sheet having excellent CTOD properties and strength and a method of manufacturing the same.
  • (Prior Art)
  • (Reference 1) Korean Laid-Open Patent Publication No. 10-2010-0066757
  • [Disclosure] [Technical Problem]
  • An aspect of the present disclosure is to provide a thick steel sheet having excellent low temperature impact toughness and CTOD properties which may be preferably applied to an offshore structural steel material, and a method of manufacturing the same.
  • However, aspects of the present disclosure are not limited thereto. Additional aspects will be set forth in part in the description which follows, and will be apparent from the description to those of ordinary skill in the related art.
  • [Technical Solution]
  • An aspect of the present disclosure relates to a thick steel sheet having excellent low temperature impact toughness and CTOD properties comprising, by weight%, 0.02 to 0.06% of C, 0.005 to 0.08% of Si, 1.0 to 2.0% of Mn, 0.01% or less of P, 0.003% or less of S, 0.001 to 0.01% of Al, 0.5 to 2.0% of Ni, 0.001 to 0.02% of Ti, 0.005 to 0.03% of Nb, 0.05 to 0.4% of Cu, 0.002 to 0.006% of N, and a balance of Fe and inevitable impurities, the thick steel sheet satisfies Equation 1 and Equation 2 below, and a microstructure comprises ferrite of 95 area% or higher, and a sum of MA and cementite of 2 area% or lower.
  • An aspect of the present disclosure relates to a method of manufacturing a thick steel sheet having excellent low temperature impact toughness and CTOD properties, the method comprising heating a slab at 1020 to 1150°C, the slab comprising, by weight%, 0.02 to 0.06% of C, 0.005 to 0.08% of Si, 1.0 to 2.0% of Mn, 0.01% or less of P, 0.003% or less of S, 0.001 to 0.01% of Al, 0.5 to 2.0% of Ni, 0.001 to 0.02% of Ti, 0.005 to 0.03% of Nb, 0.05 to 0.4% of Cu, 0.002 to 0.006% of N, and a balance of Fe and inevitable impurities, and satisfying Equation 1 and Equation 2 below; recrystallization-region rolling the heated slab at 900°C or higher; obtaining a thick steel sheet by performing a non-recrystallization-region rolling process for a finish rolling temperature to be Ar3 to 850°C after the recrystallization-region rolling; cooling the thickness steel sheet to 250°C or lower at a cooling speed of 2 to 15°C/sec; and tempering the cooled thick steel sheet at 500 to 650°C. 3.0 Mn + 2 Ni 4.3
    Figure imgb0001
    0.05 C + Si + 10 Al 0.25
    Figure imgb0002
    (in Equation 1 and Equation 2, each element symbol indicates a content of each element by weight%).
  • The above-described technical solutions do not list all the features of the present disclosure. Various features and advantages and effects thereof of the present disclosure will further be understood with reference to specific embodiments described below.
  • [Advantageous Effects]
  • According to an example embodiment in the present disclosure, excellent yield strength may be secured with respect to a thick steel sheet having a thickness of 50mm or greater, excellent impact toughness may be secured even at an extremely low temperature of about -80°C, and a thick steel sheet having impact toughness and CTOD properties at -60°C and a method of manufacturing the same may be provided, which are effects of the present disclosure.
  • [Description of Drawings]
    • FIG. 1 is an image of a microstructure of inventive example 1; and
    • FIG. 2 is graphs illustrating yield strength in accordance with an Mn+2Ni value and a CTOD value at -60°C.
    [Best Mode for Invention]
  • In the description below, preferable embodiment of the present invention will be described. However, embodiments of the present disclosure may be modified in various manners, and the scope of the present disclosure may not be limited to the embodiments described below. Also, the embodiments may be provided to more completely described the present disclosure to a person having ordinary skill in the art.
  • Thick Steel Sheet Having Excellent Low Temperature Toughness and CTOD Properties
  • Hereinafter, a thick steel sheet having excellent low temperature impact toughness and CTOD properties will be described in detail.
  • A thick steel sheet having excellent low temperature impact toughness and CTOD properties may include, by weight%, 0.02 to 0.06% of C, 0.005 to 0.08% of Si, 1.0 to 2.0% of Mn, 0.01% or less of P, 0.003% or less of S, 0.001 to 0.01% of Al, 0.5 to 2.0% of Ni, 0.001 to 0.02% of Ti, 0.005 to 0.03% of Nb, 0.05 to 0.4% of Cu, 0.002 to 0.006% of N, and a balance of Fe and inevitable impurities, and may satisfy Equation 1 and Equation 2 below, and a microstructure may include ferrite of 95 area% or higher, and a sum of MA and cementite of 2 area% or lower. 3.0 Mn + 2 Ni 4.3
    Figure imgb0003
    0.05 C + Si + 10 Al 0.25
    Figure imgb0004
    (in Equation 1 and Equation 2, each element symbol indicates a content of each element by weight%).
  • An alloy composition of the present disclosure will be described in detail. A unit of a content of each element may be wt% unless otherwise indicated.
  • C: 0.02 to 0.06%
  • C is an element which may be effective for strengthening solid solution, and may improve strength by forming Nb, and the like, and carbide.
  • When a content of C is lower than 0.02%, the above-described effect may be insufficient. When a content of C exceeds 0.06%, the formation of MA may be facilitated, and pearlite may be formed such that impact and fatigue properties at a low temperature may be deteriorated. Thus, a preferable content of C may be 0.02 to 0.06%.
  • A more preferable lower limit content of C may be 0.025%, and an even more preferable lower limit content of C may be 0.03%. A more preferable upper limit content of C may be 0.055%, and an even more preferable upper limit content of C may be 0.05%.
  • Si: 0.005 to 0.08%
  • Si is an element which may deoxidize molten steel auxiliary to Al, and may help improving yield strength and tensile strength, but may adversely affect impact and fatigue properties at a low temperature.
  • When a content of Si exceeds 0.08%, Si may interfere with dispersion of C such that the formation of MA may be facilitated, which may adversely affect impact and fatigue properties at a low temperature. Also, to control a content of Si to be 0.005% or less, a processing time of a steel making process may greatly increase, such that productivity may decrease. Thus, a preferable content of Si may be 0.005 to 0.08%.
  • A more preferable lower limit content of Si may be 0.01%, a more preferable upper limit content of Si may be 0.07%, and an even more preferable upper limit content of Si may be 0.055%.
  • Mn: 1.0 to 2.0%
  • Mn may have a great effect in increasing strength by strengthening solid solution, and thus, 1.0% or higher of Mn may be added. However, when a content of Mn is excessive, toughness may degrade due to the formation of an MnS inclusion, and the segregation of a central portion. Thus, a preferable upper limit content of Mn may be 2.0%.
  • P: 0.01% or less
  • P is an element which may cause grain boundary segregation, and may thus be a cause of weakening steel. Thus, a content of P may need to be controlled to be low as possible as P is one of impurities, and it may be preferable to control a content of P to be 0.01% or less. It may be substantially impossible to control a content of P to be 0%, and thus, 0% may not be included.
  • S: 0.003% or less
  • S may be a factor which may form an MnS inclusion by being combined with Mn, and the MnS inclusions may degrade low temperature toughness. Thus, a content of S may need to be controlled to be low as possible as S is one of impurities. It may be preferable to control a content of S to be 0.003% or less to secure low temperature toughness and low temperature fatigue properties. It may be substantially impossible to control a content of S to be 0%, and thus, 0% may not be included.
  • Al: 0.001 to 0.01%
  • Al is a main deoxidizer in the present disclosure, and it may be required to add 0.001% or higher of Al. When a content of Al exceeds 0.01%, Al may be a cause of gradation of low temperature toughness due to an increase of a fraction and a size of Al2O3 inclusion. Also, similarly to Si, Al may facilitate the formation of an MA phase in a base material and a welding heat affected portion such that low temperature toughness and low temperature fatigue properties may degrade. Thus a preferable content of Al may be 0.001 to 0.01%.
  • Ni: 0.5 to 2.0%
  • An increased content of Ni may not greatly improve strength, but Ni may improve strength and toughness at the same time.
  • When a content of Ni is lower than 0.5%, the above-described effect may be insufficient. When a content of Ni exceeds 2.0%, Ni may facilitate the formation of MA due to an increase of hardenability such that impact and CTOD toughness may be deteriorated.
  • Ti: 0.001 to 0.02%
  • Ti is an element which may form a precipitation by being combined with oxygen or nitrogen, and may accordingly prevent a structure from being coarse, and may contribute to refinement and improvement of toughness.
  • When a content of Ti is lower than 0.001%, the above-described effect may be insufficient. When a content of Ti exceeds 0.02%, Ti may become a cause of fracture due to a coarse precipitation.
  • Nb: 0.005 to 0.03%
  • Nb is an element which may prevent recrystallization during rolling or cooling by precipitating solute or carbonitride and may thus refine a structure and may increase strength.
  • When a content of Nb is lower than 0.005%, the above-described effect may be insufficient. When a content of Nb exceeds 0.03%, C concentration may occur due to C affinity, which may facilitate the formation of an MA phase and may accordingly degrade toughness and fracture properties at a low temperature.
  • Cu: 0.05 to 0.4%
  • Cu is an element which may not greatly degrade impact properties, and may improve strength by solid solution and precipitation.
  • When a content of Cu is lower than 0.05%, the above-described effect may be insufficient. When a content of Cu exceeds 0.4%, there may be a risk of surface cracks on a steel sheet by Cu heat impact.
  • N: 0.002 to 0.006%
  • N is an element which may refine an austenite structure during reheating by forming a precipitation along with Ti, Nb, Al, and the like, and may thus be helpful for improving strength and toughness. It may be preferable to add 0.002% or higher of N.
  • When a content of N exceeds 0.006%, surface cracks may be created at a high temperature, and residual N which remains after a precipitation is formed may be present in an atomic state and may decrease toughness. Thus, a preferable content of N may be 0.002 to 0.006%.
  • A remainder other than the above-described composition is Fe. However, in a general manufacturing process, inevitable impurities may be inevitably added from raw materials or a surrounding environment, and thus, impurities may not be excluded. A person skilled in the art may be aware of the impurities, and thus, the descriptions of the impurities may not be provided in the present disclosure.
  • An alloy composition of the present disclosure may need to satisfy the above-described element contents, and may also satisfy Equation 1 and Equation 2 below. 3.0 Mn + 2 Ni 4.3
    Figure imgb0005
    0.05 C + Si + 10 Al 0.25
    Figure imgb0006
    (in Equation 1 and Equation 2, each element symbol indicates a content of each element by weight%).
  • Equation 1 and Equation 2 may be to secure excellent low temperature impact toughness and CTOD properties without degradation of strength, and may be designed in consideration of correlation affecting an MA preventing effect and strength.
  • To prevent MA in accordance with Equation 2, contents of C, Si, and Al may be controlled, and to compensate for degradation of strength caused by the control of contents of the elements, Mn and Ni may need to be added in accordance with Equation 1.
  • When a value of Equation 1 is lower than 3.0, an effect of improving strength may be insufficient. When the value exceeds 4.3, low temperature impact toughness and CTOD properties may degrade.
  • A preferable value of Equation 2 may be 0.05 or higher for steel making processes such as deoxidation, and the like. When a value of Equation 2 is lower than 0.05, it may be difficult to secure strength. When the value exceeds 0.25, a large amount of MA phase may be formed such that low temperature impact toughness and CTOD properties may degrade.
  • The alloy composition of the present disclosure may further include one or more of 0.001 to 0.05% of Mo and 0.0002 to 0.005% of Ca by weight%.
  • Mo: 0.001 to 0.05%
  • Mo is an element which may be effective for improving strength by increasing hardenability. To this end, a preferable content of Mo may be 0.001% or higher. When a content of Mo exceeds 0.05%, toughness may degrade due to an increase of hardenability, and toughness may degrade by the formation of a precipitation of molybdenum carbide.
  • Ca: 0.0002 to 0.005%
  • When Ca is Al-deoxidized and added to molten steel during a steel making process, the Al-deoxidized Ca may be combined with S, mainly present as MnS, such that the formation of MnS may be prevented, and spheroidal CaS may be formed such that there may be an effect of preventing cracks in a central portion of a steel material. To this end, it may be preferable to add 0.0002% or higher of Ca. When a content of Ca exceeds 0.005%, residual Ca may be combined with O and a coarse oxidated inclusion may be formed, which may work as a crack initiation point at a low temperature due to elongation and breakage of the inclusion during a rolling process.
  • A microstructure of a thick steel sheet of the present disclosure will be described in detail.
  • A microstructure of the thick steel sheet may include ferrite of 95 area% or higher, and a sum of MA and cementite of 2 area% or lower.
  • When ferrite is 95 area% or lower, impact toughness at -80°C and CTOD properties at -60°C may degrade.
  • To secure low temperature impact toughness and CTOD properties, a structure of a base material and a fraction of MA may be important. When C is integrated and concentrated during rolling and cooling, hardenability may increase, and C may be transformed to martensite having high hardenability or may remain as austenite, which may be referred to as martensite-austenite (MA). MA may be vulnerable to fracture due to properties of high hardness, and may cause stress to be concentrated when soft ferrite around MA is transformed, and may accordingly work as initiation of fracture.
  • Also, cementite may have a characteristic similar to that of MA, and may be a hard phase having hardenability higher than that of base material acicular ferrite, and cementite may deteriorate low temperature impact toughness and CTOD properties.
  • Thus, to secure excellent low temperature impact toughness and CTOD properties, it may be important to control a sum of MA and cementite to be 2 area% or lower.
  • Ferrite has a grain size of 20 µm or less measured in equivalent circle diameter. When the grain size exceeds 20 µm, dislocation in ferrite may increase such that fracture propagation may easily occur such that low temperature impact toughness and CTOD properties may be deteriorated. The smaller the grain size, it may be more advantageous to securing low temperature impact toughness and CTOD properties, and thus, a lower limit content of ferrite may not be particularly limited.
  • Ferrite may also include polygonal ferrite and acicular ferrite, and specific fractions thereof may not be limited.
  • The thick steel sheet may have yield strength of 420MPa or higher, impact toughness of 200J or higher at -80°C, and a CTOD of 0.5mm or higher at -60°C. By securing such properties, the thick steel sheet may be appropriately applied to an offshore structural steel material used in an extremely low temperature environment. More preferably, a CTOD may be 1.0mm or higher at -60°C.
  • The thick steel sheet may have tensile strength of 500MPa or higher, an elongation rate of 25% or higher, and impact toughness of 400J or higher at -60°C.
  • The thickness steel sheet may have a thickness of 50 to 100mm.
  • Method of Manufacturing Thick Steel Sheet Having Excellent Low Temperature Impact Toughness and CTOD Properties
  • In the description below, a method of manufacturing a thick steel sheet having excellent low temperature impact toughness and CTOD properties, another aspect of the present disclosure, will be described in detail.
  • The method of manufacturing a thick steel sheet having excellent low temperature impact toughness and CTOD properties may include heating a slab comprising the above-described alloy composition at 1020 to 1150°C; recrystallization-region rolling the heated slab at 900°C or higher; obtaining a thick steel sheet by performing a non-recrystallization-region rolling process for a finish rolling temperature to be Ar3 to 850°C after the recrystallization-region rolling; cooling the thickness steel sheet to 250°C or lower at a cooling speed of 2 to 15°C/sec; and tempering the cooled thick steel sheet at 500 to 650°C.
  • Each process will be described in detail in the description below.
  • Heating Slab
  • The slab satisfying the above-described alloy composition may be heated at 1020 to 1150°C.
  • When the slab heating temperature exceeds 1150°C, an austenite grain may become coarse such that toughness may degrade. When the slab heating temperature is lower than 1020°C, sufficient solid solution of Ti, Nb, and the like may not be possible such that strength may degrade.
  • Recrystallization-Region Rolling
  • The heated slab may be recrystallization-region rolled at 900°C or higher. When the temperature is lower than 900°C, it may be difficult to implement sufficient recrystallization of austenite.
  • The recrystallization-region rolling is performed at each of the reduction ratios of the final two passes to be within 15 to 20%, which may be to secure a uniform and fine final microstructure.
  • Non-Recrystallization-Region Rolling
  • After the recrystallization-region rolling, a thick steel sheet may be obtained by performing a non-recrystallization-region rolling for a finish rolling temperature to be Ar3 to 850°C after the recrystallization-region rolling.
  • When the finish rolling temperature is lower than Ar3, a temperature of a surface of the thick steel sheet may be that of a two-phase region, and a two phase structure may be formed at a thickness of surface to 1/4t such that impact toughness may be deteriorated. When the finish rolling temperature exceeds 850°C, grain refinement may be insufficient such that strength and toughness may be deteriorated.
  • The non-recrystallization-region rolling may be performed for a thickness of the thick steel sheet to be 50 to 100mm.
  • Cooling
  • The thick steel sheet may be cooled to 250°C or lower at a cooling speed of 2 to 15°C/sec.
  • When the cooling speed exceeds 15°C/sec, there may be a difference in properties due to a difference in cooling speed between a surface and a central portion of the thick steel sheet. When the cooling speed is lower than 2°C/sec, distribution of acicular ferrite may decrease, and distribution of polygonal ferrite may increase.
  • When a cooling terminating temperature exceeds 250°C, target strength may not be satisfied.
  • Tempering
  • The cooled thick steel sheet may be tempered at 500 to 650°C. Dislocation in an MA phase and ferrite may be factors which may greatly affect low temperature impact toughness and CTOD properties. Thus, the tempering may be performed to dissolve an MA phase and to decrease dislocation in ferrite.
  • When the tempering temperature is lower than 500°C, the above-described effect may be insufficient. When the temperature exceeds 650°C, carbide may be formed, which may degrade toughness.
  • [Mode for Invention]
  • In the description below, an example embodiment of the present disclosure will be described in greater detail. It should be noted that the exemplary embodiments are provided to describe the present disclosure in greater detail, and to not limit the scope of rights of the present disclosure. The scope of rights of the present disclosure may be determined on the basis of the subject matters recited in the claims and the matters reasonably inferred from the subject matters.
  • (Embodiment)
  • Molten steel having a composition indicated in Table 1 below was prepared, and a slab was manufactured using a continuous casting process. The slab was heated, recrystallization-region rolled, non-recrystallization-region roll, and cooled and tempered under manufacturing conditions as in Table 2 below, and a thick steel sheet having a thickness of 80mm was manufactured. The recrystallization-region rolling was performed for each of reduction ratios of final two passes to be 18%.
  • A microstructure, mechanical properties, low temperature impact toughness and CTOD properties of the thick steel sheet were measured and listed in Table 3 below.
  • The microstructure was observed using a scanning electron microscope (SEM) and a transmission electron microscope (TEM), and a sum (a secondary phase) of MA and cementite was analyzed and listed in Table 3. A portion other than the secondary phase was ferrite including polygonal ferrite and acicular ferrite.
  • As for a grain size of ferrite, an average value measured in equivalent circle diameter was listed in Table 3.
  • Yield strength, tensile strength, and an elongation rate were measured through a tensile test.
  • Low temperature impact toughness was measured through a charpy impact test at -80°C and -60°C.
  • As for CTOD properties, a sample was processed to have a size of 60mm × 120mm × 300mm in perpendicular to a rolling direction in accordance with BS 7448 standards, fatigue cracks were inserted such that a fatigue crack length became 50% of a sample width, and a CTOD test was carried out at -60°C. The CTOD test was performed three times for each steel sheet, and a minimum value among the test values obtained from the three times of tests was listed in Table 3. [Table 1]
    Classification Steel Type C Si Mn P* S* Al Ni Ti Nb Cu N* Equation 1 Equation 2
    Inventive steel A 0.035 0.046 1.92 77 17 0.005 0.91 0.0091 0.006 0.28 36 3.74 0.131
    Inventive steel B 0.038 0.045 1.95 84 19 0.007 0.95 0.012 0.007 0.25 38 3.85 0.153
    Inventive steel C 0.036 0.039 1.96 75 20 0.008 0.94 0.0098 0.007 0.26 37 3.84 0.155
    Inventive steel D 0.038 0.048 1.93 65 21 0.007 0.92 0.0010 0.006 0.25 35 3.77 0.156
    Comparative steel E 0.084 0.068 1.95 84 18 0.007 0.94 0.0011 0.006 0.27 41 3.83 0.222
    Comparative steel F 0.042 0.059 1.45 82 17 0.008 0.34 0.0099 0.006 0.26 40 2.13 0.181
    Comparative steel G 0.037 0.064 2.23 91 20 0.007 1.43 0.0098 0.007 0.26 35 5.09 0.171
    Comparative steel H 0.038 0.12 1.94 94 16 0.015 0.93 0.011 0.008 0.25 32 3.8 0.308
  • In Table 1 above, a unit of each element content is weight%. Unites of P*, S*, and N* are ppm.
  • Equation 1 is a value of Mn+2Ni, Equation 2 is value of C+Si+10Al, and each element symbol indicates a content of each element by weight %. [Equation 2]
    Classification Steel Type Slab Heating Temperature (°C) Recrystal lization-Region rolling Terminating Temperature (°C) Non-Recryst allization-Region Rolling Terminating Temperature (°C) Cooling Terminating Temperature (°C) Cooling Speed (°C/s) Tempering Temperature (°C)
    Inventive example 1 A 1105 1021 775 224 3.4 552
    Inventive example 2 B 1108 1028 773 246 3.3 553
    Inventive example 3 C 1112 1030 768 187 2.8 551
    Inventive example 4 D 1110 1023 781 213 2.6 550
    Comparative example 1 A 1121 1022 875 229 3.1 551
    Comparative example 2 B 1105 1032 780 195 3.0 Not Conducted
    Comparative example 3 C 1112 1023 785 524 2.8 553
    Comparative example 4 E 1098 1030 802 195 3.1 553
    Comparative example 5 F 1103 1035 799 188 3.0 550
    Comparative example 6 G 1108 1025 786 201 2.8 547
    Comparative example 7 H 1106 1029 782 235 3.0 554
    [Table 3]
    Classification Steel Type Second ary Phase (area%) Grain Size(µm) Yield Strength (MPa) Tensile Strength (MPa) Elongation Rate (%) Impact Toughness (-60°C, J) Impact Toughness (-80°C, J) CTOD (-60 °C, mm)
    Inventive example 1 A 1.3 17.6 429 528 29 439 427 1.03
    Inventive example 2 B 1.1 18.9 435 548 29 415 348 2.42
    Inventive example 3 C 1.5 17.5 434 543 28 442 298 1.25
    Inventive example 4 D 1.3 18.6 428 529 30 435 310 1.18
    Comparative example 1 A 1.8 18.3 445 538 27 354 54 0.24
    Comparative example 2 B 1.5 38.3 432 541 28 284 28 0.31
    Comparative example 3 C 3.6 22.6 417 507 29 225 38 0.85
    Comparative example 4 E 3.8 19.5 452 585 26 129 18 0.13
    Comparative example 5 F 1.7 18.5 375 481 31 413 62 0.51
    Comparative example 6 G 5.6 19.8 486 612 25 83 15 0.11
    Comparative example 7 H 4.6 18.3 434 535 29 102 43 0.07
  • Inventive examples which satisfied the overall alloy composition and the manufacturing conditions suggested in the present disclosure secured yield strength of 420MPa or higher, impact toughness of 200J or higher at -80°C, and a CTOD value of 0.5mm or higher at -60°C, which indicate that low temperature impact toughness and CTOD properties were excellent.
  • FIG. 1 is an image of a microstructure of inventive example 1. A small amount of MA and cementite were formed, and a grain size was also fine.
  • Comparative examples 1 to 3 satisfied the alloy composition suggested in the present disclosure, but did not satisfy the manufacturing conditions.
  • As for comparative examples 1 and 2, impact toughness at -80°C and CTOD properties at -60°C were deteriorated. As for comparative example 3, impact toughness at -80°C degraded, and it was difficult to secure strength.
  • Comparative examples 4 to 7 satisfied the manufacturing conditions suggested in the present disclosure, but did not satisfy the alloy composition.
  • As for comparative example 4, a content range of C exceeded the suggested range, and as for comparative example 5, the Mn+2Ni range exceeded the suggested range such that, although strength was excellent, impact toughness at -80°C and CTOD properties at -60°C greatly degraded.
  • As for comparative example 6, a M+2Ni range was lower than the suggested range, and strength and impact toughness at -80°C were deteriorated.
  • As for comparative example 7, a range of C+Si+10Al exceeded the suggested range, and impact toughness at -80°C and CTOD properties at -60°C were greatly deteriorated.
  • FIG. 2 is graphs illustrating yield strength in accordance with an Mn+2Ni value and a CTOD value at -60°C. As indicated in FIG. 2, to secure yield strength of 420MPa or higher and a CTOD value of 0.5mm or higher, 3.0≤Mn+2Ni≤4.3 may need to be satisfied. When the Mn+2Ni value is lower than 3.0, strength decreased. When the value exceeds 4.3, a CTOD value at -60°C greatly decreased.
  • While exemplary embodiments have been shown and described above, the scope of the present disclosure is not limited thereto, and it will be apparent to those skilled in the art that modifications and variations could be made without departing from the scope of the present invention as defined by the appended claims.

Claims (11)

  1. A thick steel sheet having excellent low temperature impact toughness and CTOD properties, comprising:
    by weight%, 0.02 to 0.06% of C, 0.005 to 0.08% of Si, 1.0 to 2.0% of Mn, 0.01% or less of P, 0.003% or less of S, 0.001 to 0.01% of Al, 0.5 to 2.0% of Ni, 0.001 to 0.02% of Ti, 0.005 to 0.03% of Nb, 0.05 to 0.4% of Cu, 0.002 to 0.006% of N, and a balance of Fe and inevitable impurities,
    wherein the thick steel sheet satisfies Equation 1 and Equation 2 below, 3.0 Mn + 2 Ni 4.3
    Figure imgb0007
    0.05 C + Si + 10 Al 0.25
    Figure imgb0008
    where each element symbol indicates a content of each element by weight%, and
    wherein a microstructure comprises ferrite of 95 area% or higher, and a sum of MA and cementite of 2 area% or lower.
  2. The thick steel sheet of claim 1, wherein the thick steel sheet further comprises one or more of 0.001 to 0.05% of Mo and 0.0002 to 0.005% of Ca by weight%.
  3. The thick steel sheet of claim 1, wherein ferrite has a grain size of 20 µm or less measured in equivalent circle diameter.
  4. The thick steel sheet of claim 1, wherein ferrite comprises polygonal ferrite and acicular ferrite.
  5. The thick steel sheet of claim 1, wherein the thick steel sheet has yield strength of 420MPa or higher, impact toughness of 200J or higher at -80°C, and a CTOD of 0.5mm or higher at -60°C.
  6. The thick steel sheet of claim 1, wherein the thick steel sheet has tensile strength of 500MPa or higher, an elongation rate of 25% or higher, and impact toughness of 400J or higher at -60°C.
  7. The thick steel sheet of claim 1, wherein the thick steel sheet has a thickness of 50 to 100mm.
  8. A method of manufacturing a thick steel sheet having excellent low temperature impact toughness and CTOD properties, the method comprising:
    heating a slab at 1020 to 1150°C, the slab comprising, by weight%, 0.02 to 0.06% of C, 0.005 to 0.08% of Si, 1.0 to 2.0% of Mn, 0.01% or less of P, 0.003% or less of S, 0.001 to 0.01% of Al, 0.5 to 2.0% of Ni, 0.001 to 0.02% of Ti, 0.005 to 0.03% of Nb, 0.05 to 0.4% of Cu, 0.002 to 0.006% of N, and a balance of Fe and inevitable impurities, and satisfying Equation 1 and Equation 2 below, 3.0 Mn + 2 Ni 4.3
    Figure imgb0009
    0.05 C + Si + 10 Al 0.25
    Figure imgb0010
    where each element symbol indicates a content of each element by weight%;
    recrystallization-region rolling the heated slab at 900°C or higher;
    obtaining a thick steel sheet by performing a non-recrystallization-region rolling process for a finish rolling temperature to be Ar3 to 850°C after the recrystallization-region rolling;
    cooling the thickness steel sheet to 250°C or lower at a cooling speed of 2 to 15°C/sec; and
    tempering the cooled thick steel sheet at 500 to 650°C.
  9. The method of claim 8, wherein the slab includes one or more of 0.001 to 0.05% of Mo and 0.0002 to 0.005% of Ca by weight%.
  10. The method of claim 8, wherein the recrystallization-region rolling is performed at each of the reduction ratios of the final two passes to be within 15 to 20%
  11. The method of claim 8, wherein the non-recrystallization-region rolling is performed for a thickness of the thick steel sheet to be 50 to 100mm.
EP17885144.0A 2016-12-23 2017-12-22 Thick steel plate having excellent low-temperature impact toughness and ctod characteristic and manufacturing method therefor Active EP3561115B1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12559813B2 (en) 2019-08-23 2026-02-24 Posco Thin steel plate having excellent low-temperature toughness and CTOD properties, and method for manufacturing same
US12612674B2 (en) 2021-12-21 2026-04-28 Posco Co., Ltd Steel plate having high strength and excellent impact toughness after deformation, and method for manufacturing same

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CN119956213B (en) * 2025-01-22 2026-01-09 鞍钢股份有限公司 Low-temperature steel plate with excellent CTOD performance and manufacturing method thereof

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4313730B2 (en) * 2004-06-21 2009-08-12 株式会社神戸製鋼所 High-tensile steel plate with low material anisotropy and excellent low-temperature toughness
KR100851189B1 (en) * 2006-11-02 2008-08-08 주식회사 포스코 Steel plate for ultra high strength line pipe with excellent low temperature toughness and manufacturing method
WO2009072753A1 (en) * 2007-12-04 2009-06-11 Posco High-strength steel sheet with excellent low temperature toughness and manufacturing method thereof
KR100957968B1 (en) * 2007-12-27 2010-05-17 주식회사 포스코 High-strength, high toughness thick steel sheet with excellent substrate CT characteristics and manufacturing method
KR20100066757A (en) * 2008-12-10 2010-06-18 주식회사 포스코 Manufacturing method of steel plate with excellent ctod property
TWI365915B (en) * 2009-05-21 2012-06-11 Nippon Steel Corp Steel for welded structure and producing method thereof
JP5459166B2 (en) * 2010-09-28 2014-04-02 新日鐵住金株式会社 Steel plate for ice sea structure
JP5177310B2 (en) * 2011-02-15 2013-04-03 Jfeスチール株式会社 High tensile strength steel sheet with excellent low temperature toughness of weld heat affected zone and method for producing the same
KR20120097162A (en) * 2011-02-24 2012-09-03 현대제철 주식회사 Thick steel plate and method of manufacturing the thick steel plate
JP5304924B2 (en) * 2011-12-27 2013-10-02 Jfeスチール株式会社 Structural high-strength thick steel plate with excellent brittle crack propagation stopping characteristics and method for producing the same
KR101403224B1 (en) * 2011-12-28 2014-06-02 주식회사 포스코 Thick steel plate having excellent low yield ratio property and low temperature toughness and method for manufacturing the steel plate
JP5811032B2 (en) * 2012-05-23 2015-11-11 新日鐵住金株式会社 Steel sheet for LPG tank
US10023946B2 (en) * 2013-03-12 2018-07-17 Jfe Steel Corporation Thick steel sheet having excellent CTOD properties in multilayer welded joints, and manufacturing method for thick steel sheet
CN103741027B (en) * 2013-12-29 2015-10-28 首钢总公司 Welding joint CTOD is greater than 0. 5 millimeters of oceanographic engineering steel and preparation method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12559813B2 (en) 2019-08-23 2026-02-24 Posco Thin steel plate having excellent low-temperature toughness and CTOD properties, and method for manufacturing same
US12612674B2 (en) 2021-12-21 2026-04-28 Posco Co., Ltd Steel plate having high strength and excellent impact toughness after deformation, and method for manufacturing same

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KR20180074470A (en) 2018-07-03

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