EP4438760A1 - Steel plate having excellent heat affected zone toughness and method for manufacturing same - Google Patents
Steel plate having excellent heat affected zone toughness and method for manufacturing same Download PDFInfo
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- EP4438760A1 EP4438760A1 EP22899080.0A EP22899080A EP4438760A1 EP 4438760 A1 EP4438760 A1 EP 4438760A1 EP 22899080 A EP22899080 A EP 22899080A EP 4438760 A1 EP4438760 A1 EP 4438760A1
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- European Patent Office
- Prior art keywords
- steel material
- affected zone
- weld heat
- toughness
- zone toughness
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Classifications
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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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying 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
- C21D8/0226—Hot rolling
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying 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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- 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying 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
- C21D8/0263—Modifying 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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- 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
- C22C38/001—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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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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
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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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
- C22C38/14—Ferrous alloys, e.g. steel alloys containing 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
- C21D2211/002—Bainite
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
Definitions
- the present disclosure relates to a steel material for use in ships and the like, which has excellent toughness in a weld heat-affected zone (HAZ) formed by welding, and to a method for manufacturing the same.
- HZ weld heat-affected zone
- An icebreaker refers to a ship that sails by breaking ice on a surface of water to open a sea route.
- a steel material used in a hull of an icebreaker must have excellent impact toughness even at extremely low temperatures to withstand the low temperatures of the northern sea route, and at the same time, the steel material requires high strength to protect the hull.
- Patent Document 1 In general, in order to secure the toughness of the weld heat-affected zone manufactured with high heat input, a method of refining a grain size of the weld heat-affected zone by increasing a nitrogen content to generate fine TiN precipitates is used (Patent Document 1).
- impact toughness of a base material is likely to decrease due to free nitrogen (free N) due to the high nitrogen content thereof, and as hardenability decreases due to the reduced grain size, the tensile strength of the weld heat-affected zone decreases, and when a large amount of low-temperature transformation phase is generated, a problem of deterioration in the toughness also occurs.
- Patent Document 1 Japanese Patent Publication No. 2005-200716
- An aspect of the present disclosure is to provide a steel material capable of securing excellent toughness of a weld heat-affected zone, even when a steel material having high strength and high ductility is welded with a certain amount of heat input or more, and a method for manufacturing the same.
- a steel material having excellent toughness of a weld heat-affected zone including by weight: 0.04 to 0.07% of carbon (C), 1.5 to 1.7% of manganese (Mn), 0.1 to 0.3% of silicon (Si), 0.01 to 0.04% of aluminum (Al), 0.7 to 1.0% of nickel (Ni), 0.05 to 0.30% of molybdenum (Mo), 0.010 to 0.018% of titanium (Ti), 0.01 to 0.03% of niobium (Nb), 0.003 to 0.006% of nitrogen (N), 0.007% or less of phosphorus (P), 0.002% or less of sulfur (S), with a remainder of Fe and unavoidable impurities, wherein a weld heat-affected zone (HAZ) welded with a heat input of 100 to 200KJ/cm includes a bainite phase in an area fraction of 90% or more in a region from a fusion line (FL) to FL+3mm.
- HZ weld heat-affected zone
- a method for manufacturing a steel material having excellent toughness of a weld heat-affected zone including: reheating a steel slab having the above-described alloy composition to a temperature within a range of 1100 to 1180°C; rough rolling the heated steel slab in a temperature range of 900°C or higher; finishing rolling the steel slab in a temperature range of 800°C or higher after the rough rolling to prepare a hot-rolled steel material; and cooling the hot-rolled steel material until the temperature at t/4 point of the thickness (t, unit of mm) of the hot-rolled steel material is 600°C or lower at a cooling rate of 10°C/s or more.
- a steel material that not only has excellent strength and toughness of a base material, but also may secure excellent strength and toughness in a weld heat-affected zone, and a method of manufacturing the same may be provided.
- the steel material described above may be applied in various fields such as icebreakers, structures in extremely low-temperature environments.
- the present inventor of the present disclosure has studied in detail a technology for improving toughness formed in a weld heat-affected zone, particularly, low-temperature toughness, when welding with a medium heat input of about 100 to 200kJ/cm is performed on the steel material having high strength and toughness by increasing a welding heat input.
- the present inventor has confirmed that the technical purpose of the present disclosure may be achieved by controlling a grain size while securing a structure near a fusion line (FL) of the weld heat-affected zone as a hard state by optimizing an alloy composition and manufacturing conditions, thereby resulting in completion of the present disclosure.
- the steel material having excellent weld heat-affected zone toughness may be configured to have an alloy composition by weight: 0.04 to 0.07% of carbon (C), 1.5 to 1.7% of manganese (Mn), 0.1 to 0.3% of silicon (Si), 0.01 to 0.04% of aluminum (Al), 0.7 to 1.0% of nickel (Ni), 0.05 to 0.30% of molybdenum (Mo), 0.010 to 0.018% of titanium (Ti), 0.01 to 0.03% of niobium (Nb), 0.003 to 0.006% of nitrogen (N), 0.007% or less of phosphorus (P), and 0.002% or less of sulfur (S).
- a content of each element is based on weight, and a ratio of a structure is based on area.
- Carbon (C) is the most important element in securing strength of not only a base material but also of a weld heat-affected zone, so it needs to be contained in steel within an appropriate range.
- the C content exceeds 0.07%, hardenability improves, the strength increases excessively, and there is a problem in that toughness of the weld heat-affected zone decreases due to precipitation of fine hard phases.
- the C content is less than 0.04%, it is preferable because it causes a decrease in strength.
- C may be included in an amount of 0.04 to 0.07%. More advantageously, C may be included in an amount of 0.045% or more and 0.065% or less.
- Manganese (Mn) is a useful element for improving strength through solid solution strengthening and increasing hardenability to form a low-temperature transformation phase.
- Mn is preferably included in an amount of 1.5% or more. However, if the Mn content exceeds 1.7%, the hardenability increases excessively and there is a risk that the toughness of the weld heat-affected zone will be greatly reduced.
- Mn may be included in an amount of 1.5 to 1.7%.
- Si Silicon (Si) and Aluminum (Al) are essential elements for deoxidation by precipitating dissolved oxygen in molten steel in a form of slag during a steelmaking and continuous casting process.
- Si is preferably included in an amount of 0.1% or more
- Al is preferably included in an amount of 0.01% or more.
- Si is preferably included in an amount of 0.3% or less
- Al is preferably included in an amount of 0.04% or less.
- Nickel (Ni) is an important element improving impact toughness by facilitating cross slip of dislocations at low temperatures and increasing strength by increasing hardenability.
- the present disclosure intends to form a hard phase (preferably a bainite phase) near a fusion line in a weld heat-affected zone, and Ni is preferably included in an amount of 0.7% or more in order to improve the impact toughness in this hard phase structure.
- a hard phase preferably a bainite phase
- Ni may be included in an amount of 0.7 to 1.0%.
- Molybdenum (Mo) is an element useful for increasing strength by improving hardenability of steel, and Mo is preferably included in an amount of 0.05% or more to secure the strength targeted in the present disclosure. However, if the Mo content is excessive, the strength may increase excessively and there is a risk that toughness may decrease, so Mo is preferably included not to exceed 0.30%.
- Titanium (Ti) precipitates as TiN when reheated and suppresses grain growth in a base material and weld heat-affected zone, thereby significantly improving toughness.
- Ti is preferably included in an amount of 0.010% or more.
- the Ti content exceeds 0.018%, there is a problem in that low-temperature toughness deteriorates due to clogging of a casting nozzle or crystallization in a center portion, and a content ratio of Ti and N(N/Ti) decreases, and TiN precipitates become coarse, there is a risk that the toughness of the weld heat-affected zone may decrease.
- Ti may be included in an amount of 0.010 to 0.018%.
- Niobium (Nb) is precipitated into a form of NbC or NbCN to improve strength of a base material.
- Nb dissolved in solid solution when reheated to a high temperature precipitates very finely in a form of NbC during rolling, which has an effect of suppressing recrystallization of austenite and refining the structure.
- Nb is preferably included in an amount of 0.01% or more.
- the Nb content exceeds 0.03%, there is a high possibility that brittle cracks may be caused at an edge of the steel material, and a large amount of fine hard phases is generated, so that there is a risk that toughness may decrease.
- Nb may be included in an amount of 0.01 to 0.03%.
- N Nitrogen
- N is preferably included in an amount of 0.003% or more.
- the N content exceeds 0.006%, not only does toughness deteriorate due to generation of free nitrogen (free N), but also there is a problem that AlN precipitates and causes slab cracks.
- N may be included in an amount of 0.003 to 0.006%, and more advantageously, N may be included in an amount of 0.004% or more and 0.005% or less.
- P Phosphorus
- S Sulfur
- Phosphorus (P) and Sulfur (S) are elements causing brittleness of grain boundaries or by forming coarse inclusions to cause brittleness.
- P may be limited to 0.007% or less
- S may be limited to 0.002% or less.
- a remainder of the present disclosure may be iron (Fe).
- Fe iron
- inevitable impurities may be inevitably added from raw materials or an ambient environment, and thus, impurities may not be excluded.
- a person skilled in the art of a general manufacturing process may be aware of the impurities, and thus, the descriptions of the impurities may not be provided in the present disclosure.
- the steel material of the present disclosure having the above-described alloy composition may be composed of a single phase of bainite, bainite in an area fraction of 90% or more, and residual acicular ferrite, as a microstructure, and therefrom, the steel material has a tensile strength of 610 to 770 MPa, and impact toughness of 33J or more at - 20°C.
- the weld heat-affected zone formed by welding the steel material of the present disclosure with a medium heat input includes a bainite phase in an area fraction of 90% or more in a region from a fusion line (FL) to FL+3mm.
- bainite phase in the region of the fusion line is less than 90%, a target level of strength may not be secured.
- the region of the fusion line may be a single-phase of bainite, but may also include an acicular ferrite phase in addition to bainite.
- a trace amount of the MA phase may be included in the bainite phase and the acicular ferrite structure, and it should be noted that the MA phase contained in this case is at a level that does not impair physical properties of the fusion line.
- an average grain size of prior austenite from the fusion line (FL) to FL + 3 mm region is 100 pm or less.
- the target level of strength and toughness may be advantageously secured.
- the region from the fusion Line (FL) to FL+3 mm has a tensile strength of 610 MPa or more and impact toughness of 33 J or more at -20°C, illustrating excellent strength and low-temperature toughness.
- the steel material of the present disclosure may be manufactured through a process of reheating a steel slab satisfying the above-described composition, performing rough rolling and finishing rolling the steel slab, and then cooling the steel slab.
- reheating a steel slab satisfying the above-described composition performing rough rolling and finishing rolling the steel slab, and then cooling the steel slab.
- Reheating slab 1100 to 1180°C
- the steel slab satisfying the above-described alloy composition it is preferable to reheat the steel slab satisfying the above-described alloy composition to a temperature in a range of 1100 to 1180°C. It is preferable to set the reheating temperature to 1100°C or higher to sufficiently dissolve carbonitrides of Ti and/or Nb formed during continuous casting. However, when reheated to an excessively high temperature, there is a risk that austenite may coarsen, so the reheating temperature is preferably 1180°C or lower.
- the reheated steel slab is subjected to rough rolling to adjust a shape of the steel slab.
- the rough rolling temperature is preferably higher than a temperature (Tnr) at which austenite recrystallization stops, and accordingly, the rough rolling is preferably performed in a temperature range of 900°C or higher.
- Tnr temperature at which austenite recrystallization stops
- An effect of reducing the grain size may also be achieved through recrystallization of coarse austenite along with destruction of a casting structure such as dendrites, or the like, formed during casting by rolling.
- a total cumulative reduction ratio during rough rolling is 40% or more.
- Finishing rolling 800°C or higher
- finishing rolling is performed to manufacture a hot-rolled steel material. Specifically, it is preferable that the finishing rolling is performed in a temperature range of 800°C or higher in order to provide maximum deformation in the structure. If the finishing rolling temperature is less than 800°C, ferrite precipitates during cooling after completion of rolling and the strength decreases, so finishing rolling is preferably performed in a temperature range of 800°C or higher.
- the cumulative reduction ratio of the finishing rolling is preferably 50% or more.
- Cooling after rolling cooling is performed until the temperature at t/4 point of the thickness (t, unit of mm) of the hot-rolled steel material is 600°C or lower at a cooling rate of 10°C/s or more.
- the cooling rate is less than 10°C/s or a cooling end temperature exceeds 600°C, there is a risk that a microstructure of a base material affecting the microstructure of the weld heat-affected zone formed by subsequent welding may become coarse.
- An upper limit of the cooling rate is not specifically limited in the present disclosure, but in the technical field to which the present disclosure pertains, the cooling rate may be 100°C/s or more, so as a preferred example, the cooling rate is preferably 200°C/s or less.
- the cooling end temperature is not particularly limited, and it should be noted that the cooling is performed to room temperature.
- the cooled hot-rolled steel material may be welded, and the welding may be performed with a medium heat input, for example, may be performed with a heat input of 100 to 200 KJ/cm.
- any welding method may be used as long as it is a welding method that the above-described heat input may be applied.
- a non-limiting example may be EGW.
- the formed weld heat-affected zone has a fine structure in which the region of the fusion line is mainly composed of a bainite phase, and thus the hot-rolled steel material has excellent low-temperature toughness as well as strength.
- a steel slab having a thickness of 300 mm having the composition shown in Table 1 (a remainder of Fe and unavoidable impurities) was reheated to a temperature of 1140°C, and was then continuously subjected to rough rolling in a temperature range of 980°C, and was finished with finishing rolling in a temperature range of 880°C. Thereafter, the steel slab was cooled until the temperature at a 1/4t point reaches a temperature in a range of 470 to 580°C at a cooling rate of 16 to 35°C/s, to prepare a steel material. In this case, the rough rolling was performed at a reduction rate of 40% or more, and the finishing rolling was performed at a cumulative reduction rate of 50% or more.
- the microstructure of the steel material(base material) and the fusion line was observed using an optical microscope, and then classified using EBSD equipment, and a fraction thereof was measured.
- the tensile strength of the steel material(base material) and the fusion line was measured using a universal tensile machine, and the low-temperature impact toughness was measured through a Charpy impact absorption energy (CVN) value at -20°C using a Charpy impact tester.
- CVN Charpy impact absorption energy
- Inventive Steels 1 to 4 have excellent strength and low-temperature toughness of a weld heat-affected zone.
- the weld heat-affected zone of Inventive steels described above has a tensile strength of 610 MPa or more and an impact toughness of 33 J or more at -20°C.
- Comparative Example 1 having an excessive content of C and Mo among the alloy compositions limited by the present disclosure had inferior impact toughness as the strength of the weld heat-affected zone is excessively higher as compared to that of Inventive Steel.
- Comparative Example 2 illustrates a case in which a Mn content was insufficient, and in Comparative Example 2, the strength of the weld heat-affected zone was inferior as a bainite phase was not sufficiently formed of the weld heat-affected zone.
- Comparative Example 4 illustrates a case in which a Ti content is excessive, but N and Nb contents are insufficient, and as a result, in Comparative Example 4, coarse TiN was precipitated in a weld zone, and a particle refinement effect due to NbC was insufficient, so that a grain size of prior austenite was coarse, and as a result thereof, low-temperature toughness was inferior.
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Abstract
Description
- The present disclosure relates to a steel material for use in ships and the like, which has excellent toughness in a weld heat-affected zone (HAZ) formed by welding, and to a method for manufacturing the same.
- Recently, as the northern sea ice area is rapidly decreasing due to an increase in temperatures due to global warming, interest in opening the northern sea route is increasing. It has been observed that the temperature in the northern region has risen by 3 to 4°C over the past 50 years, and an additional increase in temperatures of 6 to 7°C is expected over the next 100 years. Due to the increase in temperatures, summer northern sea ice has decreased by about 40% since 1980, and a thickness of sea ice is also becoming thinner, thereby increasing the possibility of utilizing the northern sea route.
- It is necessary for ships to pioneer the northern sea route or to operate on the northern sea route to be built as icebreakers that can crush sea ice in the case of emergency. An icebreaker refers to a ship that sails by breaking ice on a surface of water to open a sea route.
- Most icebreakers to date have been military or exploration ships, but as interest in the northern sea route increases, the scope of use thereof is expanding to include commercial ships and cruise ships (tourist ships). For example, Russia is the country that is most active in icebreaker construction due to regional characteristics. As of 2020, about 40 icebreakers are in operation worldwide, including the Ermak, Arktika, Sivir, and the like, and the construction of icebreakers is expected to increase further in the future.
- Meanwhile, a steel material used in a hull of an icebreaker must have excellent impact toughness even at extremely low temperatures to withstand the low temperatures of the northern sea route, and at the same time, the steel material requires high strength to protect the hull.
- It is advantageous for shipbuilders to increase an amount of heat input when welding steel materials to improve productivity when constructing icebreakers. However, when an amount of welding heat input is increased, a problem in which tensile strength and toughness of a weld heat-affected zone decrease occurs, so there is a demand for steel materials in which the toughness of the weld heat-affected zone does not decrease even if the heat input during welding is increased as described above.
- In general, in order to secure the toughness of the weld heat-affected zone manufactured with high heat input, a method of refining a grain size of the weld heat-affected zone by increasing a nitrogen content to generate fine TiN precipitates is used (Patent Document 1). However, in this case, impact toughness of a base material is likely to decrease due to free nitrogen (free N) due to the high nitrogen content thereof, and as hardenability decreases due to the reduced grain size, the tensile strength of the weld heat-affected zone decreases, and when a large amount of low-temperature transformation phase is generated, a problem of deterioration in the toughness also occurs.
- Accordingly, there is a need for a technology for manufacturing steel materials that can secure the strength and toughness of the base material while also securing excellent toughness in the weld heat-affected zone even when welding is performed with increased heat input.
- (Patent Document 1)
Japanese Patent Publication No. 2005-200716 - An aspect of the present disclosure is to provide a steel material capable of securing excellent toughness of a weld heat-affected zone, even when a steel material having high strength and high ductility is welded with a certain amount of heat input or more, and a method for manufacturing the same.
- The subject of the present disclosure is not limited to the above. The subject of the present disclosure will be understood from the overall content of the present specification, and those of ordinary skill in the art to which the present disclosure pertains will have no difficulty in understanding the additional subject of the present disclosure.
- According to an aspect of the present disclosure, a steel material having excellent toughness of a weld heat-affected zone is provided, the steel material including by weight: 0.04 to 0.07% of carbon (C), 1.5 to 1.7% of manganese (Mn), 0.1 to 0.3% of silicon (Si), 0.01 to 0.04% of aluminum (Al), 0.7 to 1.0% of nickel (Ni), 0.05 to 0.30% of molybdenum (Mo), 0.010 to 0.018% of titanium (Ti), 0.01 to 0.03% of niobium (Nb), 0.003 to 0.006% of nitrogen (N), 0.007% or less of phosphorus (P), 0.002% or less of sulfur (S), with a remainder of Fe and unavoidable impurities,
wherein a weld heat-affected zone (HAZ) welded with a heat input of 100 to 200KJ/cm includes a bainite phase in an area fraction of 90% or more in a region from a fusion line (FL) to FL+3mm. - According to another aspect of the present disclosure, a method for manufacturing a steel material having excellent toughness of a weld heat-affected zone is provided, the method including: reheating a steel slab having the above-described alloy composition to a temperature within a range of 1100 to 1180°C; rough rolling the heated steel slab in a temperature range of 900°C or higher; finishing rolling the steel slab in a temperature range of 800°C or higher after the rough rolling to prepare a hot-rolled steel material; and cooling the hot-rolled steel material until the temperature at t/4 point of the thickness (t, unit of mm) of the hot-rolled steel material is 600°C or lower at a cooling rate of 10°C/s or more.
- As set forth above, according to the present disclosure, a steel material that not only has excellent strength and toughness of a base material, but also may secure excellent strength and toughness in a weld heat-affected zone, and a method of manufacturing the same may be provided. The steel material described above may be applied in various fields such as icebreakers, structures in extremely low-temperature environments.
- The various and beneficial advantages and effects of the present invention are not limited to the above-described content, and may be more easily understood through description of specific embodiments of the present disclosure.
- Terms used in the present specification are for explaining specific exemplary embodiments rather than limiting the present disclosure. In addition, a singular form used in the present specification includes a plural form also, unless the relevant definition has a clearly opposite meaning thereto.
- The meaning of "comprising" used in the specification is to embody the configuration and is not to exclude the presence or addition of other configurations.
- Unless otherwise defined, all terms including technical terms and scientific terms used in the present specification have the same meaning as would be commonly understood by a person with ordinary skill in the art to which the present disclosure pertains. Pre-defined terms are interpreted as being consistent with the relevant technical literature and the disclosure herein.
- The present inventor of the present disclosure has studied in detail a technology for improving toughness formed in a weld heat-affected zone, particularly, low-temperature toughness, when welding with a medium heat input of about 100 to 200kJ/cm is performed on the steel material having high strength and toughness by increasing a welding heat input.
- As a result thereof, the present inventor has confirmed that the technical purpose of the present disclosure may be achieved by controlling a grain size while securing a structure near a fusion line (FL) of the weld heat-affected zone as a hard state by optimizing an alloy composition and manufacturing conditions, thereby resulting in completion of the present disclosure.
- Hereinafter, the present disclosure will be described in detail.
- The steel material having excellent weld heat-affected zone toughness according to the present disclosure may be configured to have an alloy composition by weight: 0.04 to 0.07% of carbon (C), 1.5 to 1.7% of manganese (Mn), 0.1 to 0.3% of silicon (Si), 0.01 to 0.04% of aluminum (Al), 0.7 to 1.0% of nickel (Ni), 0.05 to 0.30% of molybdenum (Mo), 0.010 to 0.018% of titanium (Ti), 0.01 to 0.03% of niobium (Nb), 0.003 to 0.006% of nitrogen (N), 0.007% or less of phosphorus (P), and 0.002% or less of sulfur (S).
- Hereinafter, a reason for limiting an alloy composition of the steel material provided in the present disclosure as described above will be described in detail.
- Meanwhile, in the present disclosure, unless specifically stated, a content of each element is based on weight, and a ratio of a structure is based on area.
- Carbon (C) is the most important element in securing strength of not only a base material but also of a weld heat-affected zone, so it needs to be contained in steel within an appropriate range.
- If the C content exceeds 0.07%, hardenability improves, the strength increases excessively, and there is a problem in that toughness of the weld heat-affected zone decreases due to precipitation of fine hard phases. On the other hand, if the C content is less than 0.04%, it is preferable because it causes a decrease in strength.
- Therefore, C may be included in an amount of 0.04 to 0.07%. More advantageously, C may be included in an amount of 0.045% or more and 0.065% or less.
- Manganese (Mn) is a useful element for improving strength through solid solution strengthening and increasing hardenability to form a low-temperature transformation phase.
- In the present disclosure, since the strength of the weld heat-affected zone is intended to be secured to 610 MPa or more, to this end, Mn is preferably included in an amount of 1.5% or more. However, if the Mn content exceeds 1.7%, the hardenability increases excessively and there is a risk that the toughness of the weld heat-affected zone will be greatly reduced.
- Therefore, in the present disclosure, Mn may be included in an amount of 1.5 to 1.7%.
- Silicon (Si) and Aluminum (Al) are essential elements for deoxidation by precipitating dissolved oxygen in molten steel in a form of slag during a steelmaking and continuous casting process. When manufacturing a steel material using a converter, Si is preferably included in an amount of 0.1% or more, and Al is preferably included in an amount of 0.01% or more. However, if the content of Si and Alis excessive, since there is a risk that a coarse composite oxide of Si and Al may be generated or a large amount of fine hard phases may be generated in a microstructure of the weld heat-affected zone, Si is preferably included in an amount of 0.3% or less and Al is preferably included in an amount of 0.04% or less.
- Nickel (Ni) is an important element improving impact toughness by facilitating cross slip of dislocations at low temperatures and increasing strength by increasing hardenability.
- The present disclosure intends to form a hard phase (preferably a bainite phase) near a fusion line in a weld heat-affected zone, and Ni is preferably included in an amount of 0.7% or more in order to improve the impact toughness in this hard phase structure.
- However, if the Ni content exceeds 1.0%, there is a problem that the hardenability is excessive and the toughness is lowered, and manufacturing costs are also greatly increased. Therefore, in the present disclosure, Ni may be included in an amount of 0.7 to 1.0%.
- Molybdenum (Mo) is an element useful for increasing strength by improving hardenability of steel, and Mo is preferably included in an amount of 0.05% or more to secure the strength targeted in the present disclosure. However, if the Mo content is excessive, the strength may increase excessively and there is a risk that toughness may decrease, so Mo is preferably included not to exceed 0.30%.
- Titanium (Ti) precipitates as TiN when reheated and suppresses grain growth in a base material and weld heat-affected zone, thereby significantly improving toughness. In order to effectively precipitate TiN, Ti is preferably included in an amount of 0.010% or more. However, if the Ti content exceeds 0.018%, there is a problem in that low-temperature toughness deteriorates due to clogging of a casting nozzle or crystallization in a center portion, and a content ratio of Ti and N(N/Ti) decreases, and TiN precipitates become coarse, there is a risk that the toughness of the weld heat-affected zone may decrease.
- Therefore, in the present disclosure, Ti may be included in an amount of 0.010 to 0.018%.
- Niobium (Nb) is precipitated into a form of NbC or NbCN to improve strength of a base material. In addition, Nb dissolved in solid solution when reheated to a high temperature precipitates very finely in a form of NbC during rolling, which has an effect of suppressing recrystallization of austenite and refining the structure.
- In order to sufficiently obtain the above-described effect, Nb is preferably included in an amount of 0.01% or more. However, if the Nb content exceeds 0.03%, there is a high possibility that brittle cracks may be caused at an edge of the steel material, and a large amount of fine hard phases is generated, so that there is a risk that toughness may decrease.
- Therefore, in the present disclosure, Nb may be included in an amount of 0.01 to 0.03%.
- Nitrogen (N) combines with Ti and precipitates as TiN, thereby suppressing growth of prior austenite grains, thereby exhibiting an effect of refining a grain size. As described above, in order to form fine TiN precipitates, N is preferably included in an amount of 0.003% or more. However, if the N content exceeds 0.006%, not only does toughness deteriorate due to generation of free nitrogen (free N), but also there is a problem that AlN precipitates and causes slab cracks.
- Accordingly, N may be included in an amount of 0.003 to 0.006%, and more advantageously, N may be included in an amount of 0.004% or more and 0.005% or less.
- Phosphorus (P) and Sulfur (S) are elements causing brittleness of grain boundaries or by forming coarse inclusions to cause brittleness. For the purpose of improving resistance to brittle crack propagation of a steel material, P may be limited to 0.007% or less, and S may be limited to 0.002% or less.
- It is preferable to have 0% of these elements, but considering that these elements may inevitably be added, 0% may be excluded.
- A remainder of the present disclosure may be iron (Fe). However, in a general manufacturing process, inevitable impurities may be inevitably added from raw materials or an ambient environment, and thus, impurities may not be excluded. A person skilled in the art of a general manufacturing process may be aware of the impurities, and thus, the descriptions of the impurities may not be provided in the present disclosure.
- The steel material of the present disclosure having the above-described alloy composition may be composed of a single phase of bainite, bainite in an area fraction of 90% or more, and residual acicular ferrite, as a microstructure, and therefrom, the steel material has a tensile strength of 610 to 770 MPa, and impact toughness of 33J or more at - 20°C.
- Meanwhile, it is preferable that the weld heat-affected zone formed by welding the steel material of the present disclosure with a medium heat input (about 100 to 200 kJ/cm) includes a bainite phase in an area fraction of 90% or more in a region from a fusion line (FL) to FL+3mm.
- If the bainite phase in the region of the fusion line is less than 90%, a target level of strength may not be secured.
- The region of the fusion line may be a single-phase of bainite, but may also include an acicular ferrite phase in addition to bainite. In addition, a trace amount of the MA phase may be included in the bainite phase and the acicular ferrite structure, and it should be noted that the MA phase contained in this case is at a level that does not impair physical properties of the fusion line.
- In addition, it is preferable that an average grain size of prior austenite from the fusion line (FL) to FL + 3 mm region is 100 pm or less. As described above, by refining the grain size in the fusion line region, the target level of strength and toughness may be advantageously secured.
- Specifically, the region from the fusion Line (FL) to FL+3 mm has a tensile strength of 610 MPa or more and impact toughness of 33 J or more at -20°C, illustrating excellent strength and low-temperature toughness.
- Hereinafter, a method for manufacturing a steel material with excellent weld heat-affected zone toughness according to another aspect of the present disclosure will be described in detail.
- The steel material of the present disclosure may be manufactured through a process of reheating a steel slab satisfying the above-described composition, performing rough rolling and finishing rolling the steel slab, and then cooling the steel slab. Hereinafter, each process is described in detail.
- It is preferable to reheat the steel slab satisfying the above-described alloy composition to a temperature in a range of 1100 to 1180°C. It is preferable to set the reheating temperature to 1100°C or higher to sufficiently dissolve carbonitrides of Ti and/or Nb formed during continuous casting. However, when reheated to an excessively high temperature, there is a risk that austenite may coarsen, so the reheating temperature is preferably 1180°C or lower.
- The reheated steel slab is subjected to rough rolling to adjust a shape of the steel slab. The rough rolling temperature is preferably higher than a temperature (Tnr) at which austenite recrystallization stops, and accordingly, the rough rolling is preferably performed in a temperature range of 900°C or higher. An effect of reducing the grain size may also be achieved through recrystallization of coarse austenite along with destruction of a casting structure such as dendrites, or the like, formed during casting by rolling.
- In order to cause sufficient recrystallization and refine the structure during rough rolling at the above-described temperature, it is preferable that a total cumulative reduction ratio during rough rolling is 40% or more.
- In order to introduce an austenite structure of the rough-rolled steel sheet into a non-uniform microstructure, finishing rolling is performed to manufacture a hot-rolled steel material. Specifically, it is preferable that the finishing rolling is performed in a temperature range of 800°C or higher in order to provide maximum deformation in the structure. If the finishing rolling temperature is less than 800°C, ferrite precipitates during cooling after completion of rolling and the strength decreases, so finishing rolling is preferably performed in a temperature range of 800°C or higher.
- In order to create a fine structure as possible during finishing rolling at the above-described temperature, the cumulative reduction ratio of the finishing rolling is preferably 50% or more.
- Cooling after rolling: cooling is performed until the temperature at t/4 point of the thickness (t, unit of mm) of the hot-rolled steel material is 600°C or lower at a cooling rate of 10°C/s or more.
- When cooling the hot-rolled steel material prepared as above, when the cooling rate is less than 10°C/s or a cooling end temperature exceeds 600°C, there is a risk that a microstructure of a base material affecting the microstructure of the weld heat-affected zone formed by subsequent welding may become coarse. An upper limit of the cooling rate is not specifically limited in the present disclosure, but in the technical field to which the present disclosure pertains, the cooling rate may be 100°C/s or more, so as a preferred example, the cooling rate is preferably 200°C/s or less. In the present disclosure, the cooling end temperature is not particularly limited, and it should be noted that the cooling is performed to room temperature.
- The cooled hot-rolled steel material may be welded, and the welding may be performed with a medium heat input, for example, may be performed with a heat input of 100 to 200 KJ/cm. In this case, any welding method may be used as long as it is a welding method that the above-described heat input may be applied. A non-limiting example may be EGW.
- When the hot-rolled steel material according to the present disclosure is welded with a medium heat input, the formed weld heat-affected zone has a fine structure in which the region of the fusion line is mainly composed of a bainite phase, and thus the hot-rolled steel material has excellent low-temperature toughness as well as strength.
- Hereinafter, the present disclosure will be described in more detail through examples. However, it should be noted that the following examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure. The scope of the present disclosure may be determined by matters described in the claims and matters able to be reasonably inferred therefrom.
- A steel slab having a thickness of 300 mm having the composition shown in Table 1 (a remainder of Fe and unavoidable impurities) was reheated to a temperature of 1140°C, and was then continuously subjected to rough rolling in a temperature range of 980°C, and was finished with finishing rolling in a temperature range of 880°C. Thereafter, the steel slab was cooled until the temperature at a 1/4t point reaches a temperature in a range of 470 to 580°C at a cooling rate of 16 to 35°C/s, to prepare a steel material. In this case, the rough rolling was performed at a reduction rate of 40% or more, and the finishing rolling was performed at a cumulative reduction rate of 50% or more.
- For the steel material prepared as above, a microstructure thereof was measured and the results thereof were shown in Table 2.
- In addition, for the steel material prepared according to the above, welding was performed with a heat input of 100 to 200 KJ/cm, where a microstructure of a region from a fusion line (FL) to FL+3 mm of a weld heat-affected zone and mechanical properties (tensile strength, low-temperature impact toughness) were analyzed and the results were shown in Table 2.
- The microstructure of the steel material(base material) and the fusion line was observed using an optical microscope, and then classified using EBSD equipment, and a fraction thereof was measured.
- The tensile strength of the steel material(base material) and the fusion line was measured using a universal tensile machine, and the low-temperature impact toughness was measured through a Charpy impact absorption energy (CVN) value at -20°C using a Charpy impact tester.
[Table 1] Steel type Alloy composition (weight %) C Mn Si Al Ni Mo Nb Ti N* P* S* Inventi ve Steel 1 0.049 1.64 0.16 0.02 0.89 0.13 0.012 0.013 58 65 9 Inventi ve Steel 2 0.043 1.58 0.21 0.03 0.92 0.08 0.019 0.017 48 52 13 Inventi ve Steel 3 0.056 1.68 0.11 0.02 0.76 0.16 0.023 0.013 39 47 12 Inventi ve Steel 4 0.062 1.52 0.24 0.03 0.83 0.22 0.019 0.011 52 49 15 Compara tive Steel 1 0.093 1.66 0.16 0.03 0.91 0.32 0.016 0.015 49 68 12 Compara tive Steel 2 0.047 1.42 0.19 0.03 0.71 0.17 0.014 0.012 51 61 9 Compara tive Steel 3 0.061 1.54 0.23 0.02 0.58 0.12 0.017 0.014 49 53 8 Compara tive Steel 4 0.056 1.66 0.13 0.02 0.85 0.13 0.007 0.021 22 53 11 N*, P* and S* are expressed in ppm. [Table 2] Steel type Base material microstructur e(fraction %) Weldin g heat input (KJ/cm ) FL to FL+3mm microstructure ( fraction %) FL to +FL+3mm average AGS (µm) FL to +FL+3mm tensile strength (MPa) FL to +FL+3mm impact toughness (-20°C, B AF B remain der Inventiv e Steel 1 98 2 135 97 AF 91 635 59 Inventiv e Steel 2 100 - 168 93 AF 88 623 43 Inventiv e Steel 3 100 - 187 96 AF 97 619 59 Inventiv e Steel 4 95 5 156 92 AF 92 621 82 Comparat ive Steel 1 100 - 163 100 - 87 679 17 Comparat ive Steel 2 78 22 175 67 AF+PF 97 572 63 Comparat ive Steel 3 74 26 166 85 AF 89 598 13 Comparat ive Steel 4 98 2 171 96 AF 129 612 29 B is bainite, AF is acicular ferrite, and PF is polygonal ferrite. - As illustrated in Tables 1 to 3, in Inventive Examples 1 to 4, satisfying all of the alloy composition and manufacturing conditions limited by the present disclosure, it can be confirmed that Inventive Steels 1 to 4 have excellent strength and low-temperature toughness of a weld heat-affected zone. In particular, it can be seen that the weld heat-affected zone of Inventive steels described above has a tensile strength of 610 MPa or more and an impact toughness of 33 J or more at -20°C.
- On the other hand, in Comparative Example 1 having an excessive content of C and Mo among the alloy compositions limited by the present disclosure had inferior impact toughness as the strength of the weld heat-affected zone is excessively higher as compared to that of Inventive Steel.
- Comparative Example 2 illustrates a case in which a Mn content was insufficient, and in Comparative Example 2, the strength of the weld heat-affected zone was inferior as a bainite phase was not sufficiently formed of the weld heat-affected zone.
- In Comparative Example 3, the low-temperature toughness of the weld heat-affected zone was significantly inferior due to an insufficient Ni content, and specifically, the low-temperature toughness thereof was 13J at -20°C.
- Comparative Example 4 illustrates a case in which a Ti content is excessive, but N and Nb contents are insufficient, and as a result, in Comparative Example 4, coarse TiN was precipitated in a weld zone, and a particle refinement effect due to NbC was insufficient, so that a grain size of prior austenite was coarse, and as a result thereof, low-temperature toughness was inferior.
Claims (8)
- A steel material having excellent weld heat-affected zone toughness, comprising by weight:0.04 to 0.07% of carbon (C), 1.5 to 1.7% of manganese (Mn), 0.1 to 0.3% of silicon (Si), 0.01 to 0.04% of aluminum (Al), 0.7 to 1.0% of nickel (Ni), 0.05 to 0.30% of molybdenum (Mo), 0.010 to 0.018% of titanium (Ti), 0.01 to 0.03% of niobium (Nb), 0.003 to 0.006% of nitrogen (N), 0.007% or less of phosphorus (P), 0.002% or less of sulfur (S), a balance of Fe, and unavoidable impurities,wherein a weld heat-affected zone (HAZ) welded with a heat input of 100 to 200KJ/cm includes a bainite phase of an area fraction of 90% or more in a region from a fusion line (FL) to FL+3mm.
- The steel material having excellent weld heat-affected zone toughness of claim 1, wherein an average grain size of prior austenite in the region from the fusion line (FL) to FL+3mm is 100pm or less.
- The steel material having excellent weld heat-affected zone toughness of claim 1, wherein the region from the fusion line (FL) to FL+3mm has a tensile strength of 610 MPa or more and an impact toughness of 33J or more at -20°C.
- The steel material having excellent weld heat-affected zone toughness of claim 1, wherein the steel material comprises bainite in an area fraction of 90% or more (including 100%) and residual acicular ferrite as a microstructure.
- A method for manufacturing a steel material having excellent weld heat-affected zone toughness, comprising:reheating a steel slab including by weight: 0.04 to 0.07% of carbon (C), 1.5 to 1.7% of manganese (Mn), 0.1 to 0.3% of silicon (Si), 0.01 to 0.04% of aluminum (Al), 0.7 to 1.0% of nickel (Ni), 0.05 to 0.30% of molybdenum (Mo), 0.010 to 0.018% of titanium (Ti), 0.01 to 0.03% of niobium (Nb), 0.003 to 0.006% of nitrogen (N), 0.007% or less of phosphorus (P), 0.002% or less of sulfur (S), a balance of Fe, and unavoidable impurities, in a temperature range of 1100 to 1180°C;rough rolling the heated steel slab in a temperature range of 900°C or higher;finishing rolling the steel slab in a temperature range of 800°C or higher after the rough rolling to prepare a hot-rolled steel material; andcooling the hot-rolled steel material until the temperature at t/4 point of the thickness (t, unit of mm) of the hot-rolled steel material is 600°C or lower at a cooling rate of 10°C/s or more.
- The method for manufacturing a steel material having excellent weld heat-affected zone toughness of claim 5, wherein the rough rolling is performed at a reduction ratio of 40% or more.
- The method for manufacturing a steel material having excellent weld heat-affected zone toughness of claim 5, wherein the finish rolling is performed at a cumulative reduction ratio of 50% or more.
- The method for manufacturing a steel material having excellent weld heat-affected zone toughness of claim 5, further comprising: welding the hot-rolled steel material after the cooling,
wherein the welding is performed with a heat input of 100 to 200 KJ/cm.
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| PCT/KR2022/018814 WO2023096398A1 (en) | 2021-11-26 | 2022-11-25 | Steel plate having excellent heat affected zone toughness and method for manufacturing same |
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| US5900075A (en) * | 1994-12-06 | 1999-05-04 | Exxon Research And Engineering Co. | Ultra high strength, secondary hardening steels with superior toughness and weldability |
| JP3387371B2 (en) * | 1997-07-18 | 2003-03-17 | 住友金属工業株式会社 | High tensile steel excellent in arrestability and weldability and manufacturing method |
| JP3968011B2 (en) * | 2002-05-27 | 2007-08-29 | 新日本製鐵株式会社 | High strength steel excellent in low temperature toughness and weld heat affected zone toughness, method for producing the same and method for producing high strength steel pipe |
| US7736447B2 (en) * | 2003-12-19 | 2010-06-15 | Nippon Steel Corporation | Steel plates for ultra-high-strength linepipes and ultra-high-strength linepipes having excellent low-temperature toughness and manufacturing methods thereof |
| JP2005200716A (en) | 2004-01-16 | 2005-07-28 | Kobe Steel Ltd | Steel material superior in toughness of weld heat-affected zone |
| JP4946092B2 (en) * | 2006-02-28 | 2012-06-06 | Jfeスチール株式会社 | High-strength steel and manufacturing method thereof |
| CN101289728B (en) * | 2007-04-20 | 2010-05-19 | 宝山钢铁股份有限公司 | High-strength and high-toughness steel plate weldable with low yield strength ratio and high heat input and its manufacturing method |
| JP5096088B2 (en) * | 2007-09-13 | 2012-12-12 | 株式会社神戸製鋼所 | Welded joints with excellent toughness and fatigue cracking suppression properties |
| JP4853575B2 (en) * | 2009-02-06 | 2012-01-11 | Jfeスチール株式会社 | High strength steel pipe for low temperature excellent in buckling resistance and weld heat affected zone toughness and method for producing the same |
| JP5347827B2 (en) * | 2009-08-17 | 2013-11-20 | 新日鐵住金株式会社 | High yield point 490 MPa class welded structural steel excellent in acoustic anisotropy and method for producing the same |
| JP5857400B2 (en) * | 2009-11-25 | 2016-02-10 | Jfeスチール株式会社 | Welded steel pipe for high compressive strength line pipe and manufacturing method thereof |
| WO2011148754A1 (en) * | 2010-05-27 | 2011-12-01 | 新日本製鐵株式会社 | Process for production of thick steel sheet |
| JP4897127B2 (en) * | 2010-05-27 | 2012-03-14 | 新日本製鐵株式会社 | Manufacturing method of high strength steel sheet for welded structure |
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| JP6036616B2 (en) * | 2012-10-10 | 2016-11-30 | Jfeスチール株式会社 | Steel sheet for welded structure excellent in fatigue crack resistance and method for producing the same |
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| KR101786258B1 (en) * | 2015-12-23 | 2017-10-18 | 주식회사 포스코 | The steel sheet having high-strength and excellent heat affected zone toughness and method for manufacturing the same |
| KR102209581B1 (en) * | 2018-11-29 | 2021-01-28 | 주식회사 포스코 | The steel plate having excellent heat affected zone toughness and method for manufacturing thereof |
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