EP3239328B1 - Steel sheet for low-temperature service having excellent surface processing quality and method for manufacturing same - Google Patents
Steel sheet for low-temperature service having excellent surface processing quality and method for manufacturing same Download PDFInfo
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- EP3239328B1 EP3239328B1 EP15873529.0A EP15873529A EP3239328B1 EP 3239328 B1 EP3239328 B1 EP 3239328B1 EP 15873529 A EP15873529 A EP 15873529A EP 3239328 B1 EP3239328 B1 EP 3239328B1
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- austenite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
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- C—CHEMISTRY; METALLURGY
- 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
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/004—Dispersions; Precipitations
Definitions
- the present disclosure relates to a steel for low temperature environments having excellent surface processing qualities and a method of manufacturing the same.
- Steel used for storage containers containing liquefied natural gas, liquid nitrogen, or the like, and used for offshore platforms and facilities in polar regions may be provided as steel for low temperature environments maintaining sufficient toughness and strength even at extremely low temperatures.
- Such steel for low temperature environments should have excellent low-temperature toughness, strength, and magnetic properties, as well as having relatively low coefficients of thermal expansion and thermal conductivity.
- Patent Document 1 having excellent extreme low temperature properties through the addition of relatively large amounts of manganese (Mn) and carbon (C), with nickel (Ni) completely excluded, to stabilize austenite and including aluminum (Al) have been used.
- Patent Document 2 having excellent low-temperature toughness in such a manner that a mixed structure of austenite and epsilon martensite is secured by adding Mn thereto has been used.
- deformation behavior is implemented by slips and twin crystals in a manner different from general carbon steel.
- deformation behavior is usually implemented by slips corresponding to uniform deformation, but twin crystals corresponding to nonuniform deformation are subsequently accompanied thereby.
- size of grains is relatively large, stress required to form twin crystals is reduced, thereby easily generating twin crystals even in the case of a relatively low degree of deformation.
- deformation of twin crystals occurs in coarse grains in the early stage of deformation, thereby causing nonuniform deformation.
- WO 2014/104706 A1 discloses a high strength austenitic-based steel with remarkable toughness of a welding heat-affected zone, comprising 0.8-1.5 wt% of C, 15-22 wt% of Mn, 5 wt% or less of Cr, and the balance of Fe and other inevitable impurities, and further comprising at least one of the following (a)Mo: 0.1-1 % and B: 0.001-0.02 % and (b)Ti: 0.01-0.3 % and N: 0.003-0.1 %, the microstructure of a welding heat-affected zone comprises 90 % or more of austenite by volume fraction.
- An aspect of the present disclosure may provide steel for low temperature environments having excellent surface processing qualities and a method of manufacturing the same.
- a method of manufacturing steel for low temperature environments having excellent surface processing qualities according to Claim 1, comprising:
- steel for low temperature environments having excellent surface processing qualities even after being processed due to an austenite structure having uniform particle sizes and a method of manufacturing the same may be provided.
- the inventors recognized that, in the case of steel having an austenite structure, containing a relatively large amount of carbon (C) and manganese (Mn), partial recrystallization and grain growth of the austenite structure occurs in a rolling temperature range of the related art, thereby generating abnormally coarse austenite; in general, critical stress required to form a twin crystal is higher than that of a slip, but in a case in which a size of a grain is relatively great for the reason described above, stress required to form the twin crystal is reduced, thereby causing deformation of the twin crystal in the early state of deformation, so that a problem in which surface quality may be degraded due to discontinuous deformation may occur. In addition, the inventors have conducted in-depth research to solve the problem described above.
- steel for low temperature environments in which fine austenite is uniformly distributed may be obtained in such a manner that a titanium (Ti) -based precipitate is properly educed by adding Ti thereto, in order to suppress significant coarsening of an austenite grain and realized the present disclosure.
- the steel for low temperature environments having excellent surface processing qualities includes 15 wt% to 35 wt% of manganese (Mn), carbon (C) satisfying 23.6C+Mn ⁇ 28 and 33.5C-Mn ⁇ 23, 0.5 wt% to 5 wt% of copper (Cu) chromium (Cr) satisfying 28.5C+4.4Cr ⁇ 57 (excluding 0 wt%), 0.01 wt% to 0.5 wt% of titanium (Ti), 0.003 wt% to 0.2 wt% of nitrogen (N), iron (Fe) as a residual component, and inevitable impurities.
- Ti and N satisfy Relational Formula 1 below. 1.0 ⁇ Ti / N ⁇ 4.5 , where Mn, C, Cr, Ti, and N in each expression refer to wt% of a content of each component.
- Mn is an element playing a role in stabilizing austenite in an exemplary embodiment. 15% or more of Mn may be contained to stabilize an austenite phase at extremely low temperatures.
- an Mn content is lower than 15%, when a C content is relatively low, metastable phase epsilon martensite is formed and easily transformed into ⁇ -martensite by strain induced transformation at extremely low temperatures, thereby not securing toughness.
- the C content is increased to stabilize austenite to prevent the case described above, physical properties thereof may be dramatically degraded due to carbide precipitation.
- the Mn content may be higher than or equal to 15%.
- the Mn content is higher than 35%, a problem in which a corrosion rate of steel is increased, and economic feasibility is reduced due to an increase in the Mn content occurs.
- the Mn content is limited to a range of 15% to 35%.
- C is an element stabilizing austenite and increasing strength.
- C plays a role in reducing M s and M d , transformation points in which austenite is transformed into epsilon martensite or ⁇ -martensite by a cooling process or a process.
- M s and M d transformation points in which austenite is transformed into epsilon martensite or ⁇ -martensite by a cooling process or a process.
- stability of austenite is insufficient, thereby not obtaining stable austenite at extremely low temperatures.
- external stress causes strain induced transformation in which austenite is easily transformed into epsilon martensite or ⁇ -martensite, and toughness and the strength of steel is reduced.
- the C content is significantly high, toughness is dramatically degraded due to carbide precipitation, and workability is degraded due to a significant increase in strength.
- the C content in an exemplary embodiment may be decided in consideration of a relationship between C and other elements added thereto.
- a relationship between C and Mn in forming a carbide that the inventor has discovered is illustrated in FIG. 3 .
- the carbide is formed using C.
- C does not independently affect formation of the carbide, but affects a tendency to form the carbide in combination with Mn.
- FIG. 3 illustrates a proper C content.
- a value of 23.6C+Mn in the case of C and Mn, a content of each component is expressed using wt%) may be controlled to be higher than or equal to 28.
- the value refers to a leftward diagonal line in a hexagonal area in FIG. 3 .
- stability of austenite is decreased, and strain induced transformation is generated by impacts at extremely low temperatures, thereby degrading impact toughness.
- C is added to satisfy an entirety of Mn: 15% to 35%, 23.6C+Mn ⁇ 28, and 33.5C-Mn ⁇ 23.
- a lowermost limit of the C content is 0%, within a range satisfying the expression above.
- Cu has significantly low solid solubility in the carbide and is relatively slow in spreading in austenite, thereby being concentrated in austenite and at an interface of a nucleated carbide. Thus, spreading of C is interrupted, thereby effectively slowing carbide growth. As a result, a generation of the carbide is suppressed.
- Cu stabilizes austenite to improve extreme low-temperature toughness.
- an uppermost limit may be limited to 5%.
- the Cu content to obtain an effect of suppressing the carbide as described above is higher than or equal to 0.5%.
- Cr plays a role in improving impact toughness at low temperatures by stabilizing austenite and increasing the strength of steel through being solubilized in austenite within a range of a proper content thereof.
- Cr is an element improving corrosion resistance of steel.
- Cr is a carbide element.
- Cr is also an element forming the carbide in an austenite grain boundary to reduce the impact of low-temperatures.
- a Cr content in an exemplary embodiment may be determined in consideration of the relationship between C and other elements added thereto.
- a value of 28.5C+4.4Cr (in the case of C and Cr, a content of each component is expressed using wt%) may be controlled to be lower than or equal to 57.
- the value of 28.5C+4.4Cr is higher than 57, the generation of the carbide in the austenite grain boundary is difficult to suppress effectively, due to significant contents of Cr and C, thereby causing a problem in which impact toughness at low temperatures is degraded.
- Cr may be added to satisfy 28.5C+4.4Cr ⁇ 57.
- Ti is an element forming a TiN precipitate in combination with nitrogen (N).
- N nitrogen
- a portion of the austenite grain may be significantly coarse.
- growth of the austenite grain may be suppressed by properly educing TiN.
- at least 0.01% or more of Ti is required to be added.
- coarse TiN is educed, thereby reducing an effect of growth of the austenite grain.
- the Ti content is limited to a range of 0.01% to 0.5%.
- N is required to be added simultaneously.
- 0.003% or more of N may be added.
- solid solubility of N is lower than or equal to 0.2%, an addition of 0.2% or greater of N is significantly difficult, and 0.2% or less thereof is sufficient to educe TiN, thereby limiting an uppermost limit thereof to 0.2%.
- an N content is limited to a range of 0.003% to 0.2% in the invention.
- a residual component of an exemplary embodiment is Fe.
- unintentional impurities may be inevitably mixed from a raw material or a surrounding environment, unintentional impurities are unavoidable. Since the impurities are known to those skilled in the manufacturing process of the related art, descriptions thereof will not be provided in detail in an exemplary embodiment.
- a weight ratio of Ti to N that is, Ti/N, satisfies the Relational Formula 1 below. 1.0 ⁇ Ti / N ⁇ 4.5 ,
- the Ti/N ratio is higher than 4.5, coarse TiN is crystallized in molten steel, thereby adversely affecting a property of steel and not obtaining uniform distribution of TiN.
- surplus Ti that has not been educed to be TiN is present in a state of solid solution, thereby adversely affecting heat-affected zone toughness.
- the Ti/N ratio is lower than 1.0, an amount of solute N in a base metal is increased, thereby adversely affecting heat-affected zone toughness.
- the Ti/N ratio is controlled to be 1.0 to 4.5.
- the steel for low temperature environments according to the invention includes the TiN precipitate having a size of 0.01 ⁇ m to 0.3 ⁇ m.
- the TiN precipitate In a case in which a size of the TiN precipitate is less than 0.01 pm, the TiN precipitate is easily solubilized, so that an effect of suppressing grain growth becomes insufficient. On the other hand, in a case in which the size of the TiN precipitate is greater than 0.3 ⁇ m, an austenite grain pinning effect is reduced, and a coarse size thereof adversely affects toughness. Thus, the size of the TiN precipitate is within a range of 0.01 ⁇ m to 0.3 ⁇ m.
- the steel for low temperature environments according to the invention includes the TiN precipitate in an amount of 1.0 ⁇ 10 7 to 1.0 ⁇ 10 10 per 1 mm 2 .
- the TiN precipitate is present in an amount less than 1.0 ⁇ 10 7 per 1 mm 2 , a grain pinning effect is insignificant, thereby not effectively suppressing growth of a coarse grain.
- the TiN precipitate is present in an amount greater than 1.0 ⁇ 10 7 per 1 mm 2 , the size of the TiN precipitate becomes relatively small, so that the TiN precipitate may be unstable, and impact toughness of a material thereof may be degraded.
- the amount of the TiN precipitate is 1.0 ⁇ 10 7 to 1.0 ⁇ 10 10 per 1 mm 2 .
- the steel for low temperature environments according to the invention limits the number of coarse austenite grains having a size of 200 ⁇ m or greater in the microstructure to 5 or less per 1 cm 2 .
- the size thereof may be limited to 200 ⁇ m or greater.
- the density of a grain having a size of 200 ⁇ m or greater is greater than 5 per 1 cm 2 , due to a relatively high density of the coarse grain, nonuniform transformation is sufficiently deteriorated to affect surface qualities.
- the density of the grain having a size of 200 ⁇ m or greater is limited to 5 or less per 1 cm 2 .
- the steel for low temperature environments includes an austenite structure in an area fraction of 95% or higher.
- Austenite a representative soft structure in which ductile fracture is generated even at low temperatures, is an essential microstructure to secure low-temperature toughness and should be included in an area fraction of 95% or higher.
- austenite is not sufficient to secure low-temperature toughness, that is, impact toughness of 41 J or greater at a temperature of -196°C, so that a lowermost limit thereof is limited to 95%.
- the carbide present in the austenite grain boundary is lower than or equal to 5% in an area fraction.
- the carbide is a representative structure that may be present, beside austenite. The carbide is educed in an austenite grain boundary and becomes a cause of grain boundary rupture, thereby degrading low-temperature toughness and ductility. Thus, an uppermost limit thereof is limited to 5%.
- the method of manufacturing the steel for low temperature environments having excellent surface processing qualities includes providing a slab satisfying the alloy composition described above, heating the slab at a temperature of 1050°C to 1250°C, and manufacturing hot-rolled steel by hot rolling the slab that has been heated.
- the slab satisfying the alloy composition described above is provided.
- a reason for controlling the alloy composition is the same as described above.
- the slab is heated at the temperature of 1050°C to 1250°C.
- a process described above is performed for the sake of solution and homogenization of a cast structure, segregation, and secondary phases generated in a process of manufacturing the slab.
- the temperature is lower than 1050°C
- homogenization thereof is insufficient or a temperature of a heating furnace is significantly low, thereby causing a problem in which deformation resistance is increased during heat rolling.
- the temperature is higher than 1250°C
- partial melting may occur and surface qualities may be degraded in segregation in the cast structure, and TiN may be crystallized, thereby not contributing to austenite refinement, but degrading properties thereof.
- a heating temperature of the slab is in a range of 1050°C to 1250°C.
- the slab that has been heated is heat rolled, thereby manufacturing the hot-rolled steel.
- the alloy composition and the heating temperature of the slab, described above, may be satisfied, thereby manufacturing the steel for low temperature environments having excellent surface processing qualities.
- it is not necessary to control a condition of the manufacturing hot-rolled steel and the manufacturing hot-rolled steel may be performed using a general method.
- Inventive Examples 1 to 5 it can be confirmed that a component system and a composition range controlled in an exemplary embodiment are satisfied, and high-quality steel for low temperature environments without uneven surfaces may be obtained in such a manner that a density of a coarse austenite grain is controlled to be 5 or less per 1 cm 2 by minute eduction of TiN, and Inventive Examples 1 to 5 are processed.
- stable austenite in which fraction of austenite in the microstructure is controlled to be 95% or higher, and fraction of the carbide is controlled to be lower than 5% may be obtained, thereby securing excellent toughness at extremely low temperatures.
- Comparative Examples 1 to 3 it can be confirmed that TiN may not be educed, since Ti is not added thereto, thereby generating a coarse grain and unevenness of surfaces after Comparative Examples 1 to 3 are processed.
- Comparative Example 4 it can be confirmed that, since the component system and the composition range controlled in an exemplary embodiment are not satisfied, ferrite is generated, thereby significantly degrading impact toughness. In addition, it can be confirmed that, since a size and the number of TiN controlled in an exemplary embodiment are not satisfied, the number of coarse grains is increased, thereby generating unevenness of surfaces.
- FIG. 1A is an image of the microstructure of steel of the related art in which a nonideal coarse grain is formed by coarsening of the austenite grain.
- FIG. 1B is an image of unevenness occurring on a surface of steel after steel of FIG. 1A is tensioned. As such, it can be confirmed that, in a case in which the austenite grain is coarsened to generate the nonideal coarse grain in the microstructure of steel, surface qualities are degraded after a process thereof as described in FIG. 1B .
- FIG. 2 illustrating an image of the microstructure of Inventive Examples, uniform grains without a nonideal coarse austenite grain is formed, thereby generating excellent surface processing qualities even after the process thereof.
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Description
- The present disclosure relates to a steel for low temperature environments having excellent surface processing qualities and a method of manufacturing the same.
- Steel used for storage containers containing liquefied natural gas, liquid nitrogen, or the like, and used for offshore platforms and facilities in polar regions may be provided as steel for low temperature environments maintaining sufficient toughness and strength even at extremely low temperatures. Such steel for low temperature environments should have excellent low-temperature toughness, strength, and magnetic properties, as well as having relatively low coefficients of thermal expansion and thermal conductivity.
- Recently, steel (Patent Document 1) having excellent extreme low temperature properties through the addition of relatively large amounts of manganese (Mn) and carbon (C), with nickel (Ni) completely excluded, to stabilize austenite and including aluminum (Al) have been used. In addition, steel (Patent Document 2) having excellent low-temperature toughness in such a manner that a mixed structure of austenite and epsilon martensite is secured by adding Mn thereto has been used.
- In the case of steel for low temperature environments having austenite as a main microstructure thereof, relatively large amounts of C and Mn are added thereto, thereby stabilizing austenite. However, an addition of C and Mn affects the recrystallization behavior of austenite, thereby causing partial recrystallization and nonuniform grain growth in a rolling temperature range of the related art. Thus, only a specific small number of austenite grains are significantly grown, thereby causing significant nonuniformity in the size of austenite grains in a microstructure.
- In general, in the case of austenite structures having relatively high contents of C and Mn, deformation behavior is implemented by slips and twin crystals in a manner different from general carbon steel. In addition, in the early stage of deformation, deformation behavior is usually implemented by slips corresponding to uniform deformation, but twin crystals corresponding to nonuniform deformation are subsequently accompanied thereby. When the size of grains is relatively large, stress required to form twin crystals is reduced, thereby easily generating twin crystals even in the case of a relatively low degree of deformation. In a case in which a relatively small number of coarse grains are present in a microstructure, deformation of twin crystals occurs in coarse grains in the early stage of deformation, thereby causing nonuniform deformation. Thus, surface characteristics of materials may be deteriorated, thereby causing nonuniform thicknesses of final structures. In detail, in the case of structures requiring internal pressure resistance by securing uniform thicknesses of steel, such as low-temperature pressure vessels, significant problems in structural design and use thereof occur.
- Thus, in the case of steel, a microstructure of which has been austenitized by adding C and Mn thereto, steel for extreme low temperature environments, produced at low cost, which is economical and has secured structural stability by improving the uneven surfaces caused by early deformation of coarse grains into twin crystals is urgently required to be developed.
- Furthermore,
WO 2014/104706 A1 discloses a high strength austenitic-based steel with remarkable toughness of a welding heat-affected zone, comprising 0.8-1.5 wt% of C, 15-22 wt% of Mn, 5 wt% or less of Cr, and the balance of Fe and other inevitable impurities, and further comprising at least one of the following (a)Mo: 0.1-1 % and B: 0.001-0.02 % and (b)Ti: 0.01-0.3 % and N: 0.003-0.1 %, the microstructure of a welding heat-affected zone comprises 90 % or more of austenite by volume fraction. -
- Patent Document 1:
Korean Patent Application No. 1991-0012277 - Patent Document 2:
Japanese Patent Application No. 2007-126715 - An aspect of the present disclosure may provide steel for low temperature environments having excellent surface processing qualities and a method of manufacturing the same.
- Steel for low temperature environments having excellent surface processing qualities, comprising:
- 15 wt% to 35 wt% of manganese (Mn), carbon (C) satisfying 23.6C+Mn≥28 and 33.5C-Mn≤23, 0.5 wt% to 5 wt% of copper (Cu), chromium (Cr) satisfying 28.5C+4.4Cr≤57 and excluding 0 wt%, 0.01 wt% to 0.5 wt% of titanium (Ti), 0.003 wt% to 0.2 wt% of nitrogen (N), iron (Fe) as a residual component, and inevitable impurities,
- wherein Ti and N satisfy
Relational Formula 1 below and the steel comprises a TiN precipitate having a size of 0.01µm to 0.3µm in an amount of 1.0 x 107 to 1.0 x 1010 per 1mm2, - wherein a number of austenite grains having a size of 200 µm or greater is 5 or less per 1 cm2 in a microstructure of the steel, and
- wherein a microstructure of the steel comprises austenite in an area fraction of 95% or greater, and
- wherein a carbide present in a grain boundary of austenite is lower than or equal to 5% in an area fraction.
- A method of manufacturing steel for low temperature environments having excellent surface processing qualities according to
Claim 1, comprising: - providing a slab including 15 wt% to 35 wt% of Mn, C satisfying 23.6C+Mn≥28 and 33.5C-Mn≤23, 0.5 wt% to 5 wt% of copper Cu (excluding 0 wt%), Cr satisfying 28.5C+4.4Cr≤57 (excluding 0 wt%), 0.01 wt% to 0.5 wt% of Ti, 0.003 wt% to 0.2 wt% of N, Fe as a residual component, and inevitable impurities, Ti and N satisfying
Relational Formula 1 below; - heating the slab at a temperature of 1050°C to 1250°C; and
- manufacturing heat-rolled steel by heat rolling the slab that has been heated.
- In addition, the foregoing technical solution does not list an entirety of characteristics of the present disclosure. Various characteristics of the present disclosure and consequent advantages and effects will be understood in more detail with reference to specific exemplary embodiments below.
- According to an aspect of the present disclosure, steel for low temperature environments having excellent surface processing qualities even after being processed due to an austenite structure having uniform particle sizes and a method of manufacturing the same may be provided.
-
-
FIG. 1A is an image captured using an optical microscope, illustrating a microstructure of steel for low temperature environments of the related art. -
FIG. 1B is an image of a cross section of a specimen after steel for low temperature environments of the related art is tensioned. -
FIG. 2 is an image captured using an optical microscope, illustrating a microstructure of steel for low temperature environments according to an exemplary embodiment in the present disclosure. -
FIG. 3 is a graph illustrating ranges of carbon (C) and manganese (Mn) controlled in an exemplary embodiment. - The inventors recognized that, in the case of steel having an austenite structure, containing a relatively large amount of carbon (C) and manganese (Mn), partial recrystallization and grain growth of the austenite structure occurs in a rolling temperature range of the related art, thereby generating abnormally coarse austenite; in general, critical stress required to form a twin crystal is higher than that of a slip, but in a case in which a size of a grain is relatively great for the reason described above, stress required to form the twin crystal is reduced, thereby causing deformation of the twin crystal in the early state of deformation, so that a problem in which surface quality may be degraded due to discontinuous deformation may occur. In addition, the inventors have conducted in-depth research to solve the problem described above.
- Thus, the inventors confirmed that steel for low temperature environments in which fine austenite is uniformly distributed may be obtained in such a manner that a titanium (Ti) -based precipitate is properly educed by adding Ti thereto, in order to suppress significant coarsening of an austenite grain and realized the present disclosure.
- Hereinafter, steel for low temperature environments having excellent surface processing qualities according to an exemplary embodiment will be described in detail.
- The steel for low temperature environments having excellent surface processing qualities includes 15 wt% to 35 wt% of manganese (Mn), carbon (C) satisfying 23.6C+Mn≥28 and 33.5C-Mn≤23, 0.5 wt% to 5 wt% of copper (Cu) chromium (Cr) satisfying 28.5C+4.4Cr≤57 (excluding 0 wt%), 0.01 wt% to 0.5 wt% of titanium (Ti), 0.003 wt% to 0.2 wt% of nitrogen (N), iron (Fe) as a residual component, and inevitable impurities. In addition, Ti and N satisfy
Relational Formula 1 below. - First, an alloy composition of the steel for low temperature environments having excellent surface processing qualities according to the invention will be described in detail. Hereinafter, a unit of each alloying element is wt%.
- Mn is an element playing a role in stabilizing austenite in an exemplary embodiment. 15% or more of Mn may be contained to stabilize an austenite phase at extremely low temperatures. In other words, in a case in which an Mn content is lower than 15%, when a C content is relatively low, metastable phase epsilon martensite is formed and easily transformed into α-martensite by strain induced transformation at extremely low temperatures, thereby not securing toughness. In a case in which the C content is increased to stabilize austenite to prevent the case described above, physical properties thereof may be dramatically degraded due to carbide precipitation. Thus, the Mn content may be higher than or equal to 15%. On the other hand, in a case in which the Mn content is higher than 35%, a problem in which a corrosion rate of steel is increased, and economic feasibility is reduced due to an increase in the Mn content occurs. Thus, the Mn content is limited to a range of 15% to 35%.
- C is an element stabilizing austenite and increasing strength. In detail, C plays a role in reducing Ms and Md, transformation points in which austenite is transformed into epsilon martensite or α-martensite by a cooling process or a process. Thus, in a case in which C is insufficiently added, stability of austenite is insufficient, thereby not obtaining stable austenite at extremely low temperatures. In addition, external stress causes strain induced transformation in which austenite is easily transformed into epsilon martensite or α-martensite, and toughness and the strength of steel is reduced. On the other hand, in a case in which the C content is significantly high, toughness is dramatically degraded due to carbide precipitation, and workability is degraded due to a significant increase in strength.
- In detail, the C content in an exemplary embodiment may be decided in consideration of a relationship between C and other elements added thereto. To this end, a relationship between C and Mn in forming a carbide that the inventor has discovered is illustrated in
FIG. 3 . As illustrated inFIG. 3 , the carbide is formed using C. C does not independently affect formation of the carbide, but affects a tendency to form the carbide in combination with Mn. -
FIG. 3 illustrates a proper C content. In order to prevent the carbide from being generated, on a premise that other components satisfy a range made in an exemplary embodiment, a value of 23.6C+Mn (in the case of C and Mn, a content of each component is expressed using wt%) may be controlled to be higher than or equal to 28. The value refers to a leftward diagonal line in a hexagonal area inFIG. 3 . In a case in which 23.6C+Mn is lower than 28, stability of austenite is decreased, and strain induced transformation is generated by impacts at extremely low temperatures, thereby degrading impact toughness. In a case in which the C content is significantly high, that is, 33.5C-Mn is higher than 23, an addition of a significant amount of C causes carbide precipitation, thereby degrading low-temperature impact toughness. In conclusion, C is added to satisfy an entirety of Mn: 15% to 35%, 23.6C+Mn≥28, and 33.5C-Mn≤23. As illustrated inFIG. 3 , a lowermost limit of the C content is 0%, within a range satisfying the expression above. - Cu has significantly low solid solubility in the carbide and is relatively slow in spreading in austenite, thereby being concentrated in austenite and at an interface of a nucleated carbide. Thus, spreading of C is interrupted, thereby effectively slowing carbide growth. As a result, a generation of the carbide is suppressed. In addition, Cu stabilizes austenite to improve extreme low-temperature toughness. However, in a case in which a Cu content is higher than 5%, hot workability of steel is degraded. Thus, an uppermost limit may be limited to 5%. In addition, the Cu content to obtain an effect of suppressing the carbide as described above is higher than or equal to 0.5%.
- Cr plays a role in improving impact toughness at low temperatures by stabilizing austenite and increasing the strength of steel through being solubilized in austenite within a range of a proper content thereof. In addition, Cr is an element improving corrosion resistance of steel. However, Cr is a carbide element. In detail, Cr is also an element forming the carbide in an austenite grain boundary to reduce the impact of low-temperatures. Thus, a Cr content in an exemplary embodiment may be determined in consideration of the relationship between C and other elements added thereto. In order to prevent the carbide from being generated, on a premise that other components satisfy a range made in an exemplary embodiment, a value of 28.5C+4.4Cr (in the case of C and Cr, a content of each component is expressed using wt%) may be controlled to be lower than or equal to 57. In a case in which the value of 28.5C+4.4Cr is higher than 57, the generation of the carbide in the austenite grain boundary is difficult to suppress effectively, due to significant contents of Cr and C, thereby causing a problem in which impact toughness at low temperatures is degraded. Thus, Cr may be added to satisfy 28.5C+4.4Cr ≤ 57.
- Ti is an element forming a TiN precipitate in combination with nitrogen (N). In an exemplary embodiment, during high-temperature hot rolling, a portion of the austenite grain may be significantly coarse. Thus, growth of the austenite grain may be suppressed by properly educing TiN. To this end, at least 0.01% or more of Ti is required to be added. However, in a case in which a Ti content is higher than 0.5%, an effect of growth of the austenite grain may not be improved anymore. In addition, coarse TiN is educed, thereby reducing an effect of growth of the austenite grain. Thus, in the invention, the Ti content is limited to a range of 0.01% to 0.5%.
- In an exemplary embodiment, in order to effectively achieve a goal of adding Ti described above, N is required to be added simultaneously. In detail, in order to effectively educe TiN, 0.003% or more of N may be added. However, since solid solubility of N is lower than or equal to 0.2%, an addition of 0.2% or greater of N is significantly difficult, and 0.2% or less thereof is sufficient to educe TiN, thereby limiting an uppermost limit thereof to 0.2%. Thus, an N content is limited to a range of 0.003% to 0.2% in the invention.
- A residual component of an exemplary embodiment is Fe. However, since, in a manufacturing process of the related art, unintentional impurities may be inevitably mixed from a raw material or a surrounding environment, unintentional impurities are unavoidable. Since the impurities are known to those skilled in the manufacturing process of the related art, descriptions thereof will not be provided in detail in an exemplary embodiment.
-
- In a case in which a Ti/N ratio is controlled to be higher than or equal to 1.0, solute Ti is combined with N, thereby educing minute TiN. In addition, since TiN that has been educed using a method described above is stably present, the growth of the austenite grain may be effectively suppressed.
- However, in a case in which the Ti/N ratio is higher than 4.5, coarse TiN is crystallized in molten steel, thereby adversely affecting a property of steel and not obtaining uniform distribution of TiN. In addition, surplus Ti that has not been educed to be TiN is present in a state of solid solution, thereby adversely affecting heat-affected zone toughness. However, in a case in which the Ti/N ratio is lower than 1.0, an amount of solute N in a base metal is increased, thereby adversely affecting heat-affected zone toughness. Thus, the Ti/N ratio is controlled to be 1.0 to 4.5.
- In addition, the steel for low temperature environments according to the invention includes the TiN precipitate having a size of 0.01µm to 0.3µm.
- In a case in which a size of the TiN precipitate is less than 0.01 pm, the TiN precipitate is easily solubilized, so that an effect of suppressing grain growth becomes insufficient. On the other hand, in a case in which the size of the TiN precipitate is greater than 0.3 µm, an austenite grain pinning effect is reduced, and a coarse size thereof adversely affects toughness. Thus, the size of the TiN precipitate is within a range of 0.01 µm to 0.3 µm.
- In addition, the steel for low temperature environments according to the invention includes the TiN precipitate in an amount of 1.0×107 to 1.0×1010 per 1 mm2.
- In a case in which the TiN precipitate is present in an amount less than 1.0×107 per 1 mm2, a grain pinning effect is insignificant, thereby not effectively suppressing growth of a coarse grain. On the other hand, in a case in which the TiN precipitate is present in an amount greater than 1.0×107 per 1 mm2, the size of the TiN precipitate becomes relatively small, so that the TiN precipitate may be unstable, and impact toughness of a material thereof may be degraded. Thus, the amount of the TiN precipitate is 1.0×107 to 1.0×1010 per 1 mm2.
- In addition, the steel for low temperature environments according to the invention limits the number of coarse austenite grains having a size of 200 µm or greater in the microstructure to 5 or less per 1 cm2.
- Since, in the case of austenite having a grain size less than 200 pm, stress required to generate the twin crystal is sufficiently higher than stress required to generate a slip, nonuniform transformation is not generated within a transformation rate of steel for low temperature environments of the related art when a structure is manufactured. Thus, the size thereof may be limited to 200 µm or greater. In addition, in a case in which the density of a grain having a size of 200 µm or greater is greater than 5 per 1 cm2, due to a relatively high density of the coarse grain, nonuniform transformation is sufficiently deteriorated to affect surface qualities. Thus, the density of the grain having a size of 200 µm or greater is limited to 5 or less per 1 cm2.
- In the meantime, the steel for low temperature environments according to an exemplary embodiment includes an austenite structure in an area fraction of 95% or higher. Austenite, a representative soft structure in which ductile fracture is generated even at low temperatures, is an essential microstructure to secure low-temperature toughness and should be included in an area fraction of 95% or higher. In a case in which austenite is included in an area fraction of lower than 95%, austenite is not sufficient to secure low-temperature toughness, that is, impact toughness of 41 J or greater at a temperature of -196°C, so that a lowermost limit thereof is limited to 95%.
- In addition, the carbide present in the austenite grain boundary is lower than or equal to 5% in an area fraction. In an exemplary embodiment, the carbide is a representative structure that may be present, beside austenite. The carbide is educed in an austenite grain boundary and becomes a cause of grain boundary rupture, thereby degrading low-temperature toughness and ductility. Thus, an uppermost limit thereof is limited to 5%.
- Hereinafter, a method of manufacturing the steel for low temperature environments having excellent surface processing qualities according to the invention will be described in detail.
- The method of manufacturing the steel for low temperature environments having excellent surface processing qualities according to another exemplary embodiment includes providing a slab satisfying the alloy composition described above, heating the slab at a temperature of 1050°C to 1250°C, and manufacturing hot-rolled steel by hot rolling the slab that has been heated.
- The slab satisfying the alloy composition described above is provided. A reason for controlling the alloy composition is the same as described above.
- The slab is heated at the temperature of 1050°C to 1250°C.
- A process described above is performed for the sake of solution and homogenization of a cast structure, segregation, and secondary phases generated in a process of manufacturing the slab. In a case in which the temperature is lower than 1050°C, homogenization thereof is insufficient or a temperature of a heating furnace is significantly low, thereby causing a problem in which deformation resistance is increased during heat rolling. In a case in which the temperature is higher than 1250°C, partial melting may occur and surface qualities may be degraded in segregation in the cast structure, and TiN may be crystallized, thereby not contributing to austenite refinement, but degrading properties thereof. Thus, a heating temperature of the slab is in a range of 1050°C to 1250°C.
- The slab that has been heated is heat rolled, thereby manufacturing the hot-rolled steel.
- In an exemplary embodiment, the alloy composition and the heating temperature of the slab, described above, may be satisfied, thereby manufacturing the steel for low temperature environments having excellent surface processing qualities. Thus, in detail, it is not necessary to control a condition of the manufacturing hot-rolled steel and the manufacturing hot-rolled steel may be performed using a general method.
- Hereinafter, the present disclosure will be described in more detail through exemplary embodiments. However, an exemplary embodiment below is intended to describe the present disclosure in more detail through illustration thereof, but not limit the scope of rights of the present invention, because the scope of rights thereof is determined by the contents written in the appended claims and can be reasonably inferred therefrom.
- After a slab satisfying a component system stated in Table 1 below is manufactured in the same manner as a manufacturing condition stated in Table 2, a microstructure, yield strength, an elongation rate, Charpy impact toughness at a temperature of -196°C, or the like, are measured to be stated in Table 2 or Table 3, respectively.
- In Table 3 below, unevenness of surfaces is assessed by observing surfaces of the steel for low temperature environments with the naked eye.
[Table 1] Classification C Mn Cu Cr N Ti Weight Ratio of Ti/N 23.6C+Mn 33.5C-Mn 28.5C+4.4Cr Comparative Example 1 0.62 18.12 0.12 0.2 0.012 32.8 2.7 18.6 Comparative Example 2 0.37 25.4 1.12 3.85 0.018 34.1 -13.0 27.5 Comparative Example 3 0.61 18.13 1.5 1.25 0.012 32.5 2.3 22.9 Comparative Example 4 0.31 28.7 0.15 1.32 0.025 0.024 0.96 36.0 -18.3 14.6 Comparative Example 5 0.45 11.7 0.008 0.07 8.75 22.3 3.4 12.8 Comparative Example 6 0.37 24.1 1.02 3.5 0.011 0.05 4.55 32.8 -11.7 25.9 Inventive Example 1 0.58 21.7 0.61 0.55 0.053 0.06 1.13 35.388 -2.3 19.0 Inventive Example 2 0.45 24.3 0.43 3.08 0.12 0.17 1.42 34.92 -9.2 26.4 Inventive Example 3 0.39 28.6 0.85 3.45 0.016 0.02 1.25 37.804 -15.5 26.3 Inventive Example 4 0.44 27.5 0.42 1.62 0.024 0.04 1.67 37.884 -12.8 19.7 Inventive Example 5 1.1 23.4 1.05 0.87 0.021 0.05 2.38 49.36 13.5 35.2 - In Table 1 above, a unit of a content of each element is wt%.
[Table 2] Classi ficati on Temper ature of Heatin g Furnac e (°C) Austenite Fraction (%) Carbide Fractio n (%) TiN Size(µm) No. of TiN (No./mm2 ) Density of Coarse Grain of 200 µm or greater (No./cm2) Comparative Example 1 1195 99.1 0.9 10 Comparative Example 2 1180 99.6 0.4 7 Comparative Example 3 1200 99 1 8 Comparative Example 4 1195 98.9 0.8 0.003 1.2X104 7 Comparative Example 5 1200 82 1 1.25 4.32X105 7 Comparative Example 6 1195 99.6 0 0.95 5.2X106 9 Inventive Example 1 1205 99.1 0.8 0.013 5.3X108 0 Inventive Example 2 1190 99.3 0 0.015 4.2X108 0 Inventive Example 3 1195 99.4 0 0.022 2.9X108 1 Inventive Example 4 1198 99.6 0 0.012 5.4X108 0 Inventive Example 5 1203 98.7 0.8 0.025 2.7X108 0 [Table 3] Classi ficati on Yield Strength (MPa) Tensile Strength (MPa) Elongation Rate (%) Base Metal Impact Value (J, -196°C) Unevenness of Surfaces Comparative Example 1 363 1011 69 83 Occurred Comparative Example 2 470 931 46 130 Occurred Comparative Example 3 405 1006 57 81 Occurred Comparative Example 4 411 912 57 130 Occurred Comparative Example 5 346 762 12 38 Occurred Comparative Example 6 360 926 54 35 Occurred Inventive Example 1 425 980 67 153 Not Occurred Inventive Example 2 453 902 58 148 Not Occurred Inventive Example 3 468 975 61 165 Not Occurred Inventive Example 4 427 980 65 152 Not Occurred Inventive Example 5 481 971 51 118 Not Occurred - In Inventive Examples 1 to 5, it can be confirmed that a component system and a composition range controlled in an exemplary embodiment are satisfied, and high-quality steel for low temperature environments without uneven surfaces may be obtained in such a manner that a density of a coarse austenite grain is controlled to be 5 or less per 1 cm2 by minute eduction of TiN, and Inventive Examples 1 to 5 are processed. In addition, stable austenite in which fraction of austenite in the microstructure is controlled to be 95% or higher, and fraction of the carbide is controlled to be lower than 5% may be obtained, thereby securing excellent toughness at extremely low temperatures.
- On the other hand, in Comparative Examples 1 to 3, it can be confirmed that TiN may not be educed, since Ti is not added thereto, thereby generating a coarse grain and unevenness of surfaces after Comparative Examples 1 to 3 are processed.
- In detail, in the case of Comparative Example 4, it can be confirmed that, since the component system and the composition range controlled in an exemplary embodiment are not satisfied, ferrite is generated, thereby significantly degrading impact toughness. In addition, it can be confirmed that, since a size and the number of TiN controlled in an exemplary embodiment are not satisfied, the number of coarse grains is increased, thereby generating unevenness of surfaces.
- In addition, in the case of Comparative Examples 5 to 6, it can be confirmed that Ti and N within a range controlled in an exemplary embodiment are added, but the weight ratio of Ti to N and a size and the number of the TiN precipitate do not satisfy the range controlled in an exemplary embodiment, so that coarse TiN is educed, and the coarse grain is significantly generated to generate unevenness of surfaces after Comparative Examples 5 to 6 are processed.
-
FIG. 1A is an image of the microstructure of steel of the related art in which a nonideal coarse grain is formed by coarsening of the austenite grain.FIG. 1B is an image of unevenness occurring on a surface of steel after steel ofFIG. 1A is tensioned. As such, it can be confirmed that, in a case in which the austenite grain is coarsened to generate the nonideal coarse grain in the microstructure of steel, surface qualities are degraded after a process thereof as described inFIG. 1B . However, inFIG. 2 , illustrating an image of the microstructure of Inventive Examples, uniform grains without a nonideal coarse austenite grain is formed, thereby generating excellent surface processing qualities even after the process thereof. - While exemplary embodiments have been shown and described above, 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 (3)
- Steel for low temperature environments having excellent surface processing qualities, comprising:15 wt% to 35 wt% of manganese (Mn), carbon (C) satisfying 23.6C+Mn≥28 and 33.5C-Mn≤23, 0.5 wt% to 5 wt% of copper (Cu), chromium (Cr) satisfying 28.5C+4.4Cr≤57 and excluding 0 wt%, 0.01 wt% to 0.5 wt% of titanium (Ti), 0.003 wt% to 0.2 wt% of nitrogen (N), iron (Fe) as a residual component, and inevitable impurities,wherein Ti and N satisfy Relational Formula 1 below and the steel comprises a TiN precipitate having a size of 0.01µm to 0.3µm in an amount of 1.0 x 107 to 1.0 x 1010 per 1mm2,wherein a number of austenite grains having a size of 200 µm or greater is 5 or less per 1 cm2 in a microstructure of the steel, andwherein a microstructure of the steel comprises austenite in an area fraction of 95% or greater, and
- The steel for low temperature environments having excellent surface processing qualities of claim 1, wherein the Charpy impact toughness of the steel is higher than or equal to 41 J at a temperature of -196°C.
- A method of manufacturing steel for low temperature environments having excellent surface processing qualities according to Claim 1, comprising:providing a slab including 15 wt% to 35 wt% of Mn, C satisfying 23.6C+Mn≥28 and 33.5C-Mn≤23, 0.5 wt% to 5 wt% of copper Cu (excluding 0 wt%), Cr satisfying 28.5C+4.4Cr≤57 (excluding 0 wt%), 0.01 wt% to 0.5 wt% of Ti, 0.003 wt% to 0.2 wt% of N, Fe as a residual component, and inevitable impurities, Ti and N satisfying Relational Formula 1 below;heating the slab at a temperature of 1050°C to 1250°C; and
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