WO2015012317A1 - ラインパイプ用鋼板及びラインパイプ - Google Patents

ラインパイプ用鋼板及びラインパイプ Download PDF

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WO2015012317A1
WO2015012317A1 PCT/JP2014/069471 JP2014069471W WO2015012317A1 WO 2015012317 A1 WO2015012317 A1 WO 2015012317A1 JP 2014069471 W JP2014069471 W JP 2014069471W WO 2015012317 A1 WO2015012317 A1 WO 2015012317A1
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steel
plate thickness
thickness
plate
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PCT/JP2014/069471
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English (en)
French (fr)
Japanese (ja)
Inventor
篠原　康浩
原　卓也
泰志 藤城
土井　直己
直史 鮎川
英一 山下
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新日鐵住金株式会社
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Priority to BR112015029358-1A priority Critical patent/BR112015029358B1/pt
Priority to RU2015151179A priority patent/RU2623569C1/ru
Priority to JP2014551471A priority patent/JP5748032B1/ja
Priority to CN201480022395.3A priority patent/CN105143489B/zh
Priority to KR1020157031046A priority patent/KR101709887B1/ko
Priority to EP14829550.4A priority patent/EP3026140B1/en
Publication of WO2015012317A1 publication Critical patent/WO2015012317A1/ja

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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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/002—Bainite
    • 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
    • C21D2211/005—Ferrite
    • 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
    • C21D2211/008—Martensite
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese

Definitions

  • the present invention relates to a steel plate for line pipe and a line pipe.
  • Sour resistance refers to hydrogen-induced crack resistance (HIC resistance) (Hydrogen-Induced Cracking Resistance) and sulfide stress crack resistance (SSC resistance) (Sulfide crack resistance) in a corrosive environment containing hydrogen sulfide. ).
  • HIC resistance hydrogen-induced crack resistance
  • SSC resistance sulfide stress crack resistance
  • the submarine line pipe is generally required to be a thick steel pipe having a thickness of 25 mm or more and to have a high circumferential compressive strength.
  • a welded steel pipe for a high compressive strength sour line pipe having a bainite fraction of 80% or more and excellent compressive strength has been proposed (for example, see Patent Document 3 below).
  • a thick steel plate for example, a steel plate having a thickness of 25 mm or more
  • the reduction in the recrystallized region and the non-recrystallized region becomes insufficient, and the toughness evaluation, particularly the drop weight tear test (Drop In the toughness evaluation by Weight Tear Test (DWTT), it may be difficult to ensure characteristics (hereinafter also referred to as “DWTT characteristics”).
  • DWTT characteristics characteristics
  • a method of producing a thick steel plate for a sour line pipe excellent in DWTT characteristics by generating a multiphase structure of fine ferrite and 70% or more of bainite has been proposed (for example, the following) (See Patent Document 4).
  • Patent Document 1 Japanese Patent Laid-Open No. 62-1112722
  • Patent Document 2 Japanese Patent Laid-Open No. 61-165207
  • Patent Document 3 Japanese Patent Laid-Open No. 2011-132600
  • Patent Document 4 Japanese Patent Laid-Open No. 2010-189722
  • the present invention has been made in view of the above circumstances, and is excellent in HIC resistance (particularly HIC resistance in a sour environment of pH 5.0 or higher), and a steel sheet for line pipes having both compressive strength and DWTT characteristics, And it is providing the line pipe manufactured using this steel plate for line pipes.
  • the present inventors have intensively investigated the conditions that should be satisfied by a steel sheet for line pipes that has excellent HIC resistance (particularly HIC resistance in a sour environment of pH 5.0 or higher) and that has both compressive strength and DWTT characteristics. To complete the present invention. That is, specific means for solving the above problems are as follows.
  • the ferrite fraction (F2) in the structure at the plate thickness 1/2 position is 5 to 60%, and the balance is a structure composed of bainite or a structure composed of bainite and martensite.
  • the ratio (F1 / F2) of the ferrite fraction (F1) to the ferrite fraction (F2) is 1.00 to 5.00,
  • the average particle diameter of ferrite at the position of 1/4 of the plate thickness is 2.0 to 15.0 ⁇ m, and the average particle diameter of ferrite at the position of 1/2 of the plate thickness is 5.0 to 20.0 ⁇ m.
  • the hardness at the plate thickness 1/2 position is 400 Hv or less, and the length of MnS at the plate thickness 1/2 position is 1.00 mm or less, A steel plate for line pipes having a thickness of 25 mm or more.
  • a steel plate for line pipes having excellent HIC resistance particularly HIC resistance in a sour environment of pH 5.0 or higher
  • having both compressive strength and DWTT characteristics are used.
  • a line pipe manufactured in this way is provided.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • “%” indicating the content of a component (element) means “% by mass”.
  • the “plate thickness 1 ⁇ 2 position” refers to a position corresponding to 1 ⁇ 2 of the plate thickness of the steel plate, that is, the plate thickness center portion of the steel plate.
  • the “plate thickness 1 ⁇ 4 position” means that the distance in the plate thickness direction from the plate thickness central portion (plate thickness 1 ⁇ 2 position) of the steel plate is 1 ⁇ 4 of the plate thickness. Point to a position.
  • content of C (carbon) may be described as "C amount”. Other elements may be similarly described.
  • the steel plate for line pipes of the present invention (hereinafter also simply referred to as “steel plate”) is mass%, C: 0.040 to 0.080%, Si: 0.05 to 0.40%, Mn: 1.60. ⁇ 2.00%, P: 0.020% or less, S: 0.0025% or less, Mo: 0.05-0.20%, Ca: 0.0011-0.0050%, Al: 0.060% Nb: 0.010 to 0.030%, Ti: 0.008 to 0.020%, N: 0.0015 to 0.0060%, and O: 0.0040% or less,
  • the content ratio of [Ca / S] is 0.90 to 2.70
  • the content ratio of Ti to N [Ti / N] is 2.20 or more
  • the balance consists of Fe and inevitable impurities
  • Ceq defined by the following formula (1) is 0.380 to 0.480
  • the thickness is 1/4 position.
  • the ferrite fraction (F1) is 20 to 60% and the balance is composed of bainite
  • the ferrite fraction (F2) at the thickness 1/2 position is 5 to 60% and the balance is composed of bainite.
  • a structure consisting of bainite and martensite, a ratio (F1 / F2) of the ferrite fraction (F1) to the ferrite fraction (F2) is 1.00 to 5.00
  • the average particle diameter of ferrite at a position of 1/4 thickness is 2.0 to 15.0 ⁇ m
  • the average particle diameter of ferrite at a position of 1/2 sheet thickness is 5.0 to 20.0 ⁇ m
  • the sheet thickness is 1/2
  • the hardness of the position is 400 Hv or less
  • the length of MnS at the position of 1/2 the plate thickness is 1.00 mm or less
  • the plate thickness is 25 mm or more.
  • Ceq C + Mn / 6 + (Ni + Cu) / 15 + (Cr + Mo + V) / 5 (1)
  • C, Mn, Ni, Cu, Cr, Mo, and V represent the mass% of each element, respectively.
  • the steel sheet of the present invention has the above-described configuration, the HIC resistance (particularly the HIC resistance under an environment of pH 5.0 or higher) is improved, and the compressive strength and the DWTT characteristics can be compatible.
  • the present invention has been made based on the following examination results.
  • the present inventors examined various conditions that steel materials should have to prevent hydrogen-induced cracking (HIC) from occurring under a sour environment with a pH of 5.0 or higher using various steel plates having different compositions. .
  • HIC hydrogen-induced cracking
  • the sour resistance was evaluated by examining the occurrence of HIC and the HIC fracture surface rate (hereinafter also referred to as “HIC test CAR”).
  • HIC test CAR HIC fracture surface rate
  • the steel sheet was immersed in a solution of pH 5.0 saturated with hydrogen sulfide gas (for example, “Solution B” of NACE TM0284), and the HIC fracture surface ratio (CAR of the HIC test) after 96 hours was examined. Was done by. If the HIC fracture surface ratio was 5% or less, the sour resistance was good.
  • HIC is generated starting from elongated MnS (hereinafter also referred to as “extended MnS” or simply “MnS”), which is present at the position of half the plate thickness. It was determined that it was over 1.00 mm. Therefore, it has been found that by controlling the length of MnS at the position of 1/2 the plate thickness to 1.00 mm or less, generation of HIC can be suppressed in a sour environment having a pH of 5.0 or more.
  • extended MnS elongated MnS
  • the present inventors have found that the following conditions are necessary to reduce the length of MnS to 1.00 mm or less. That is, the S amount is 0.0025% or less, and the content ratio [Ca / S] is 0.90 to 2.70.
  • the present inventors have clarified that when the content ratio [Ca / S] is less than 0.90, the length of MnS may not be controlled to 1.00 mm or less. Further, when the content ratio [Ca / S] is more than 2.70, the present inventors form coarse aggregates of Ca-based oxides, and HIC is generated starting from the aggregates. Clarified that there may be cases.
  • the present inventors have found that HIC can be suppressed in a sour environment having a pH of 5.0 or more by setting the hardness at the position of 1/2 the thickness of the steel sheet to 400 Hv or less. Furthermore, as a result of investigating the relationship between the hardness at the plate thickness 1/2 position and the ferrite fraction in detail, when the ferrite fraction of the structure at the plate thickness 1/2 position is higher than 60%, the hardness of the steel sheet is 400 Hv. I found out that it might exceed. The reason for this is considered to be that when ferrite is generated at a position of 1/2 the plate thickness, the C content is concentrated in the remainder, and as a result, bainite or martensite containing a high C content is formed. That is, in the steel sheet of the present invention, the hardness at the position of half the plate thickness is 400 Hv or less by setting the ferrite fraction at the position of half the plate thickness to 60% or less.
  • the center segregation portion refers to a portion having the highest Mn concentration when the Mn concentration distribution in the plate thickness direction of the steel sheet is measured by EPMA (Electron Probe Micro Analyzer).
  • the measurement method of the hardness in a board thickness 1/2 position and a ferrite fraction (F1, F2) is as showing in the below-mentioned Example.
  • the steel structure for satisfying compressive strength, DWTT characteristics, and HIC resistance was intensively studied.
  • the ferrite fraction (F1) at the 1/4 position of the plate thickness should be set to 20 to 60%
  • the ferrite fraction (F2) at the 1/2 position of the plate thickness should be set to 5 to 60%.
  • the compressive strength has a high correlation with the ferrite fraction (F1), and the compressive strength decreases as the soft ferrite fraction increases at the 1/4 thickness position.
  • the ferrite fraction (F1) and the ferrite fraction (F2) each exceed 60% the reduction in compressive strength becomes significant.
  • the steel sheet of the present invention exhibits high compressive strength when the ferrite fraction (F1) and the ferrite fraction (F2) are each 60% or less.
  • the DWTT characteristic of a steel plate improves as the ferrite fraction of the steel plate increases. In order to exert such an effect, it was found that the ferrite fraction (F1) in the steel sheet should be 20% or more and the ferrite fraction (F2) should be 5% or more.
  • the inventors of the present invention have a ratio of the ferrite fraction (F1) at the 1/4 thickness position and the ferrite fraction (F2) at the 1/2 thickness position. It has been found that (F1 / F2) may be 1.00 or more. That is, the steel sheet of the present invention has both the compressive strength and the DWTT characteristic when the ratio (F1 / F2) is 1.00 or more. When the ratio (F1 / F2) is less than 1.00, in particular, the DWTT characteristic is deteriorated (see, for example, Comparative Example 6 described later). As a result of the above examination, in the present invention, the ratio (F1 / F2) is set to 1.00 or more. Moreover, since it is difficult to manufacture the ratio (F1 / F2) exceeding 5.00, the ratio (F1 / F2) is set to 5.00 or less in the present invention.
  • the ratio (F1 / F2) in a normal steel sheet, is less than 1.00 for the following reason. That is, normally, in the cooling process after rolling to obtain a steel plate, the slowest cooling rate is at the plate thickness 1/2 position (plate thickness center). For this reason, in a normal steel plate, the ferrite fraction is highest in the plate thickness direction at the plate thickness 1/2 position. Therefore, in a normal steel plate, the ratio (F1 / F2) is less than 1.00 (see, for example, Comparative Example 6 described later). However, the present inventors have made the cooling rate (V1) at the 1/4 position of the plate thickness slower than the cooling rate (V2) at the 1/2 position of the plate thickness in the temperature range of 600 to 700 ° C.
  • the ratio (F1 / F2) was successfully made 1.00 or more.
  • the ratio (F1 / F2) may be 1.00 to 5.00, and the production method (for example, the cooling method after rolling) is not particularly limited.
  • the remaining part at the position of the quarter thickness is a structure made of bainite. Thereby, generation
  • the compressive strength of the steel sheet is determined by measuring the compressive strength in the circumferential direction of the steel pipe after forming the steel sheet (line pipe) into a steel pipe (line pipe) and then performing coating heating for the purpose of corrosion prevention. Or by measuring the compressive strength of the steel sheet subjected to the treatment corresponding to the pipe making and the coating heating, as shown in the examples described later. This is because crushing of a steel pipe such as a line pipe has the highest correlation with the circumferential compressive strength of the steel pipe.
  • the compressive strength in the circumferential direction of the steel pipe is greatly reduced by the Bauschinger effect due to pipe making, but the strength is restored when the coating is heated. This recovery is due to so-called static strain aging in which C (carbon) during coating heating diffuses into dislocations introduced during pipe making to create a Cottrell atmosphere.
  • the present inventors have conducted intensive investigations on alloy elements that exhibit static strain aging. As a result, it was found that Mo is effective as such an alloy element.
  • the reason why Mo is effective as the alloy element is considered as follows. That is, since Mo has a weak interaction with C, Mo fixes a large amount of C in the steel sheet containing Mo. However, the above interaction is further weakened by heating, and the C atom moves away from the Mo atom and moves to the dislocation. It is considered that static strain aging is exhibited by such movement.
  • the Mo amount is set to 0.05% or more.
  • the inventors newly found that if the amount of Mo is too large, the hardness at the plate thickness 1/2 position (plate thickness center) is remarkably increased, so that the upper limit of the amount of Mo is preferably 0.20%. I found out.
  • the present invention made based on the above examination results will be described in detail below.
  • the steel sheet of the present invention has C (carbon): 0.040 to 0.080%, Si (silicon): 0.05 to 0.40%, Mn (manganese): 1.60 to 2.00%, P ( Phosphorus): 0.020% or less, S (sulfur): 0.0025% or less, Mo (molybdenum): 0.05 to 0.20%, Ca (calcium): 0.0011 to 0.0050%, Al ( Aluminum): 0.060% or less, Nb (niobium): 0.010 to 0.030%, Ti (titanium): 0.008 to 0.020%, N (nitrogen): 0.0015 to 0.0060% And O (oxygen): 0.0040% or less, the content ratio [Ca / S] is 0.90 to 2.70, and the content ratio [Ti / N] is 2.20 or more.
  • C 0.040 to 0.080% C is an element that improves the strength of steel. From the viewpoint of this effect, the lower limit of the C amount is 0.040%. On the other hand, if the amount of C exceeds 0.080%, the formation of carbides is promoted and the HIC resistance is impaired. For this reason, the upper limit of the C amount is 0.080%. Moreover, in order to suppress deterioration of HIC resistance, weldability, and toughness, the upper limit of the C content is preferably 0.060%.
  • Si 0.05 to 0.40% Si is a deoxidizing element. From the viewpoint of this effect, the lower limit of the Si amount is 0.05%. On the other hand, if the amount of Si exceeds 0.40%, the toughness (hereinafter also referred to as “HAZ toughness”) of the heat affected zone (HAZ) decreases. For this reason, the upper limit of the Si amount is set to 0.40%.
  • Mn 1.60 to 2.00%
  • Mn is an element that improves strength and toughness. From the viewpoint of this effect, the lower limit of the amount of Mn is 1.60%. On the other hand, when the amount of Mn exceeds 2.00%, HAZ toughness will fall. For this reason, the upper limit of the amount of Mn is 2.00%. In order to suppress HIC, the Mn content is preferably less than 1.75%.
  • P 0.020% or less
  • P is an impurity.
  • the content exceeds 0.020%, the HIC resistance is impaired, and the toughness of HAZ is reduced. Therefore, the P content is limited to 0.020% or less.
  • the smaller the amount of P the better. Therefore, the lower limit of the amount of P is not particularly limited.
  • the amount of P is preferably 0.001% or more from the viewpoint of manufacturing cost.
  • S 0.0025% or less
  • S is an element that reduces the HIC resistance by generating MnS that extends in the rolling direction during hot rolling. Therefore, in the present invention, it is necessary to reduce the S amount, and the S amount is limited to 0.0025% or less. Since the smaller the amount of S, the better.
  • the lower limit of the amount of S is not particularly limited. However, the amount of S may be 0.0008% or more from the viewpoint of manufacturing costs and manufacturing restrictions of secondary refining.
  • Mo 0.05-0.20%
  • Mo is an element that improves hardenability and at the same time forms carbonitride to improve strength.
  • Mo is contained from a viewpoint which promotes the static strain aging at the time of the coating heating after making it a steel pipe (line pipe), and ensures high compressive strength.
  • the lower limit of the Mo amount is set to 0.05%.
  • the upper limit of the amount of Mo is made 0.20%.
  • Ca 0.0011 to 0.0050%
  • Ca is an element that produces sulfide CaS, suppresses the production of MnS extending in the rolling direction, and contributes significantly to the improvement of HIC resistance.
  • the lower limit of the Ca content is 0.0011%.
  • the upper limit of the Ca content is 0.0050% or less.
  • Al 0.060% or less
  • Al is an element usually contained as a deoxidizing element. However, when there is too much Al content, inclusions will increase and ductility and toughness will be impaired. For this reason, the upper limit of the amount of Al is 0.060%.
  • Al is also an element that promotes the formation of a mixed structure of MA (Martensite Austenite). From the viewpoint of reducing the MA fraction, the Al content is preferably 0.008% or less. Further, if the Al content is 0.008% or less, it is advantageous in terms of improving HAZ toughness.
  • the amount of Al is preferably 0.0002% or more from the viewpoint of more effectively obtaining the effect as a deoxidizing element.
  • Al is intentionally contained in steel, it may be mixed as an impurity in steel.
  • the lower the amount of Al the better, so there is no particular limitation on the lower limit of the amount of Al.
  • Nb 0.010 to 0.030%
  • Nb is an element that forms carbides and nitrides and contributes to improvement in strength.
  • Nb amount shall be 0.010% or more.
  • the Nb content is 0.030% or less.
  • the Nb amount is preferably 0.020% or less.
  • Ti 0.008 to 0.020%
  • Ti is an element usually used as a deoxidizer or nitride-forming element for refining crystal grains.
  • the Ti amount is set to 0.008% or more.
  • Ti is also an element that lowers toughness due to the formation of coarse carbonitrides. Therefore, in the present invention, the amount of Ti is limited to 0.020% or less.
  • N 0.0015 to 0.0060%
  • N nitrogen
  • the N content is set to 0.0015% or more in order to make the austenite grain size during heating using nitrides fine.
  • the upper limit of the N amount is set to 0.0060%.
  • the content ratio [Ti / N] of Ti with respect to N is important in order to make the austenite grain size during heating fine.
  • content ratio [Ti / N] shall be 2.20 or more.
  • the content ratio [Ti / N] is preferably 3.00 or more.
  • the content ratio [Ti / N] is preferably 5.00 or less, and more preferably 4.00 or less, from the viewpoint of further suppressing toughness deterioration due to excessive Ti carbide.
  • O is an impurity element.
  • the amount of O is regulated to 0.0040% or less. Since the smaller the amount of O, the lower the amount of O is not particularly limited. However, the O amount may be 0.0010% or more from the viewpoint of manufacturing cost and manufacturing restrictions.
  • Ceq 0.380 to 0.480 Ceq is an amount defined by the following formula (1).
  • Ceq C + Mn / 6 + (Ni + Cu) / 15 + (Cr + Mo + V) / 5 (1)
  • C, Mn, Ni, Cu, Cr, Mo, and V are respectively C (carbon), Mn (manganese), Ni (nickel), Cu (copper), Cr (chromium), The content (mass%) of each element of Mo (molybdenum) and V (vanadium) is represented.
  • Ni, Cu, Cr, and V are arbitrary elements, and each content may be 0%. The preferable content of these optional elements will be described later.
  • Ceq defined by the above formula (1) is limited to 0.380 to 0.480.
  • the strength of the line pipe obtained by the steel plate of the present invention is lowered.
  • the line pipe cannot satisfy the required tensile strength (520 MPa or more) of strength grade X60 or more.
  • Ceq exceeds 0.480 toughness (for example, DWTT characteristics) and sour resistance (for example, HIC resistance) deteriorate. Therefore, in the present invention, Ceq is limited to 0.380 to 0.480.
  • the inevitable impurities refer to components contained in raw materials or components mixed in during the manufacturing process and not intentionally contained in the steel.
  • unavoidable impurities specifically, Sb (antimony), Sn (tin), W (tungsten), Co (cobalt), As (arsenic), Pb (lead), Bi (bismuth), B (boron), H (hydrogen) is mentioned.
  • Sb, Sn, W, Co, and As are mixed with a content of 0.1% or less
  • Pb and Bi are mixed with a content of 0.005% or less
  • B and H have a content of 0.00.
  • the steel plate of the present invention has Ni (nickel): 0.50% or less, Cr (chromium): 0.50% or less, Cu (copper): 0.50% or less, Mg (magnesium): 0.0050%.
  • REM rare earth element
  • V vanadium
  • the steel sheet of the present invention may contain one or more of Ni: 0.50% or less, Cr: 0.50% or less, and Cu: 0.50% or less.
  • These elements may be mixed as inevitable impurities in the steel in addition to the intentional inclusion in the steel. Therefore, there is no particular limitation on the lower limit of the content of these elements.
  • these elements and preferable contents when the steel sheet of the present invention contains these elements will be described.
  • Ni 0.50% or less
  • Ni (nickel) is an element effective for improving toughness and strength.
  • the Ni content is preferably 0.50% or less.
  • the Ni content is preferably 0.05% or more.
  • Cr 0.50% or less Cr (chromium) is an effective element for improving the strength of steel by precipitation strengthening. However, if the amount of Cr is too large, hardenability is increased, bainite becomes excessive, and toughness may be reduced. Therefore, the Cr content is preferably 0.50% or less. On the other hand, the Cr content is preferably 0.05% or more.
  • Cu 0.50% or less
  • Cu is an element effective for increasing strength without decreasing toughness. However, if the amount of Cu is too large, cracks are likely to occur during heating of the steel piece or during welding. Accordingly, the Cu content is preferably 0.50% or less. On the other hand, the amount of Cu is preferably 0.05% or more.
  • Mg 0.0050% or less
  • Mg is an element effective as a deoxidizing agent and a desulfurizing agent.
  • Mg is an element that generates fine oxides and contributes to improvement of HAZ toughness.
  • the Mg amount is preferably 0.0050% or less.
  • the Mg content is preferably 0.0001% or more.
  • REM 0.0050% or less
  • “REM” means a rare earth element, Sc (scandium), Y (yttrium), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (Neodymium), Pm (promethium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb It is a general term for 17 elements consisting of (ytterbium) and Lu (lutetium). Further, “REM: 0.0050% or less” indicates that the total content of the 17 elements is 0.0050% or less.
  • the amount of REM is an element effective as a deoxidizer and a desulfurizer. However, if the amount of REM is too large, coarse oxides are formed, which may lead to deterioration of HIC resistance and toughness of the base material and HAZ. Therefore, the amount of REM is preferably 0.0050% or less. On the other hand, the amount of REM is preferably 0.0001% or more.
  • V 0.100% or less
  • V is an element that forms carbides and nitrides and contributes to improvement in strength.
  • the V amount is preferably 0.100% or less.
  • the V amount is preferably 0.010% or more.
  • the steel sheet of the present invention has a ferrite fraction (F1) in the structure at the 1/4 position of the plate thickness of 20% or more, and the ferrite fraction (F2) in the structure at the 1/2 position of the plate thickness. Is 5% or more, the DWTT characteristics are improved. When at least one of the ferrite fraction (F1) is less than 20% and the ferrite fraction (F2) is less than 5%, the DWTT characteristics deteriorate.
  • the steel sheet of the present invention has an improved compressive strength when the ferrite fraction (F1) is 60% or less and the ferrite fraction (F2) is 60% or less.
  • the compressive strength decreases.
  • the steel sheet of the present invention has both compressive strength and DWTT characteristics when the ratio (F1 / F2) is 1.00 or more.
  • the ratio (F1 / F2) is less than 1.00, the DWTT characteristic is particularly deteriorated.
  • the ratio (F1 / F2) is 1.00 or more and 5.00 or less, preferably more than 1.00 and 5.00 or less, and more preferably 1.05 or more and 5.00 or less.
  • the steel sheet of the present invention has a hardness at a plate thickness 1/2 position of 400 Hv or less and a length of MnS at a plate thickness 1/2 position of 1.00 mm or less. Thereby, the HIC resistance is improved. It is also advantageous for DWTT characteristics.
  • the length of MnS at the 1/2 position of the plate thickness is 1.00 mm or less, but it is more preferable that the length satisfies the following formula (2) from the viewpoint of further improving the HIC resistance.
  • Length of MnS at the position of 1/2 of the plate thickness ⁇ 10 ⁇ (1350-X) / 350 ⁇ / 1000 (2)
  • X is the hardness (Hv) at the position of 1/2 the plate thickness, and is a value of 400 (Hv) or less]
  • the maximum Mn segregation degree of the center segregation part of the steel slab is 2.2 or less
  • the center segregation part A method of manufacturing a steel sheet by sequentially subjecting a steel piece having a thickness of 1.0 mm or less to reheating, thick plate rolling (coarse rolling and finish rolling), and cooling treatment. A preferable aspect of each treatment will be described later.
  • the average grain size of ferrite at a position of 1/4 of the plate thickness is 2.0 to 15.0 ⁇ m.
  • the average particle diameter of the ferrite at the 1/4 position of the plate thickness is 15.0 ⁇ m or less, the DWTT characteristic is improved.
  • An increase in rolling load is suppressed when the average grain size of ferrite at the position of 1/4 of the plate thickness is 2.0 ⁇ m or more, which is advantageous in terms of manufacturing cost.
  • the average grain size of ferrite at the position of 1/2 the plate thickness is 5.0 to 20.0 ⁇ m.
  • the average particle diameter of the ferrite at the position of 1/2 the plate thickness is 20.0 ⁇ m or less, the DWTT characteristic is improved. If the average grain size of ferrite at the position of 1/2 the plate thickness is 5.0 ⁇ m or more, an increase in rolling load is suppressed, which is advantageous in terms of manufacturing cost.
  • board thickness of the steel plate of this invention is 25 mm or more. Thereby, high compressive strength is ensured.
  • the plate thickness is preferably more than 25 mm, more preferably 30 mm or more, further preferably 32 mm or more, and particularly preferably 35 mm or more.
  • board thickness can be 45 mm or less, for example.
  • the steel plate of the present invention can be manufactured by making a steel slab by continuous casting after melting in the steel making process, and sequentially subjecting the steel slab to reheating, thick plate rolling, and cooling.
  • the thickness of the steel slab is preferably 300 mm or more because it is easy to obtain a steel plate having a thickness of 25 mm or more.
  • the reheating temperature when reheating the steel slab is preferably 950 ° C. or higher from the viewpoint of further improving the HIC resistance.
  • it is preferable that the said reheating temperature is 1150 degrees C or less from a viewpoint which suppresses deterioration of DWTT characteristic more.
  • the average rolling reduction per pass is 10% or more and 120 mm or more in a recrystallization temperature range (for example, a temperature range exceeding 900 ° C.). Setting the average rolling reduction per pass to 10% or more is advantageous in that the recrystallization of austenite is promoted and the particle size can be reduced. Moreover, rough rolling to 120 mm or more is advantageous in that the cumulative reduction amount can be increased in the subsequent non-recrystallization zone rolling. That is, when the cumulative reduction amount in the non-recrystallization zone rolling is increased, many dislocations can be introduced into the austenite grains.
  • the dislocations introduced into the austenite grains serve as nucleation sites for transformation to ferrite in the subsequent cooling process, thus contributing to the refinement of the grain size.
  • finish rolling in a non-recrystallized region (for example, a temperature region of 750 to 900 ° C.) to a final plate thickness of 25 mm or more.
  • Cooling (for example, water cooling) after the plate rolling is preferably performed at a cooling start temperature of 700 to 820 ° C.
  • Setting the cooling start temperature to 700 ° C. or higher makes it easy to reduce the ferrite fraction (F2) at the plate thickness 1/2 position to 60% or less, and the maximum altitude at the plate thickness 1/2 position to 400 Hv or less. It is advantageous in that it is easy.
  • Setting the cooling start temperature to 820 ° C. or less is advantageous in that the ferrite fraction (F2) can be easily adjusted to 5% or more and the DWTT characteristics can be easily improved.
  • the cooling rate in the said cooling shall be 10 degrees C / s or more from a viewpoint of improving an intensity
  • the cooling stop temperature is preferably 200 ° C. or higher from the viewpoint of further suppressing the HIC at the position of 1/2 the plate thickness and further suppressing the deterioration of toughness. Further, the cooling stop temperature is preferably 450 ° C. or lower from the viewpoint of further improving the strength.
  • the cooling rate (V1) at the 1/4 thickness position is preferably lower than the cooling rate (V2) at the 1/2 thickness position in the temperature range of 600 to 700 ° C.
  • the ferrite generation amount at the 1/4 position of the plate thickness can be made higher than the ferrite generation amount at the 1/2 position of the plate thickness, so that the ratio (F1 / F2) can be easily adjusted to 1.00 or more.
  • the cooling rate (V1) is faster than the cooling rate (V2). Therefore, in the obtained steel plate, the ratio (F1 / F2) is less than 1.00. Yes.
  • the cooling is preferably performed at a cooling rate (V3) in a temperature range of 600 ° C. or lower at 15 ° C./s or higher.
  • the line pipe of the present invention is a steel pipe manufactured using the steel plate for line pipes of the present invention. Therefore, the line pipe of the present invention is excellent in HIC resistance (particularly, HIC resistance in an environment of pH 5.0 or higher) and has both compressive strength and DWTT characteristics in the same manner as the steel sheet of the present invention. Yes.
  • the line pipe of the present invention can be produced by a known pipe making method using the steel sheet for line pipe of the present invention as a material.
  • Known pipe making methods include UOE forming method, JCOE forming method, and the like.
  • the steel slab obtained above is heated to 950 to 1150 ° C. (however, 1180 ° C. in Comparative Example 2), and rough rolling is performed at over 900 ° C. and an average reduction of 10% or more (however, 8% in Comparative Example 3).
  • Until the thickness became 120 mm or more (however, 100 mm in Comparative Example 4), and then finish-rolled to the final thickness in the non-recrystallization temperature range of 900 ° C. or less (however, 930 ° C. in Comparative Example 5).
  • accelerated cooling water cooling
  • accelerated cooling water cooling
  • accelerated cooling water cooling
  • the cooling rate (V1) at the plate thickness of 1/4 position in the temperature range of 600 to 700 ° C. where ferrite is generated. ) was controlled to be slower than the cooling rate (V2) at the plate thickness 1/2 position.
  • the water-cooling zone through which the steel plate after finish rolling passes is subdivided, and a zone for discharging water and a zone for not discharging water are set, and the steel plate is intermittently water-cooled.
  • V1 was made faster than V2 by continuously water cooling the steel sheet in the same manner as in the normal steel sheet manufacturing method.
  • the ferrite fraction (ferrite area ratio) and the ferrite particle size (average particle size of ferrite) were obtained by image processing, and the remaining structure was specified.
  • Image processing was performed using a small general-purpose image analyzer LUZEX AP manufactured by Nireco Corporation.
  • the average particle diameter of the ferrite was determined by calculating the equivalent circle diameter for 30 ferrites and simply averaging the obtained 30 equivalent circle diameters.
  • the ferrite fraction F1 at the plate thickness 1/4 position, the ferrite fraction F2 at the plate thickness 1/2 position, the ferrite grain size at the plate thickness 1/4 position, and the plate thickness 1/2 shown in Table 3 below.
  • the ferrite grain size at each position was determined, and the remaining structure at the 1/4 position of the plate thickness and the remaining structure at the 1/2 position of the plate thickness as shown in Table 3 were specified.
  • FIG. 1 shows, as an example, an optical micrograph (magnification 500 times) of a cross-section (cross-section after polishing and corrosion with a repeller reagent) at a half-thickness position in the steel plate of Invention Example 10.
  • ratio [F1 / F2] was determined based on the ferrite fraction (F1) at the 1/4 position of the plate thickness and the ferrite fraction (F2) at the 1/2 position of the plate thickness.
  • a specimen for a tensile test was taken from the steel sheet so that the width direction of the steel sheet and the longitudinal direction of the specimen were parallel.
  • the shape of the test piece was a flat plate conforming to the American Petroleum Institute Standard API 5L (hereinafter simply referred to as “API 5L”).
  • API 5L American Petroleum Institute Standard API 5L
  • the collected test piece was subjected to a tensile test at room temperature in accordance with API 5L. Based on the maximum load in this tensile test, the tensile strength was determined.
  • the compressive strength was measured by the following method in order to evaluate the properties in the circumferential direction of the steel pipe after the steel sheet was made into a steel pipe (line pipe) and heated for painting for the purpose of corrosion prevention.
  • a wide specimen full thickness specimen
  • a pre-strain of 2% was applied to the collected wide test piece in order to give a strain equivalent to pipe making.
  • the compression test piece was extract
  • the compression test piece has a cylindrical shape with a diameter of 22 mm and a length of 66 mm, includes a central portion of the thickness of the steel plate, and has a width direction of the steel plate and a longitudinal direction of the compression test piece (test direction of the compression test). Collected in parallel.
  • the collected compression test piece was heat-treated in a salt bath at 220 ° C. for 5 minutes, and the compression test piece after the heat treatment was subjected to a compression test in accordance with ASTM E9-09. The 0.5% offset proof stress in the compression test was determined as the yield strength (compression strength).
  • CAR of HIC test A test piece (full thickness test piece) for evaluating HIC resistance was collected from the steel sheet. The collected specimen was immersed in a solution of “Solution B” of NACE TM0284 for 96 hours, and the presence or absence of HIC was measured with an ultrasonic flaw detector for the immersed specimen. Based on the measurement results, the crack area ratio (CAR) was determined. In this evaluation, the smaller the CAR (most preferably 0%), the better the HIC resistance.
  • the composition of steel 8 to steel 10 which is an example of the present invention, but the ferrite fraction (F1), the ferrite fraction (F2), the ratio [F1 / F2], the balance at the 1/4 position of the plate thickness Texture, remaining structure at 1/2 thickness, ferrite grain size at 1/4 thickness, ferrite grain size at 1/2 thickness, hardness at 1/2 thickness, and 1/2 thickness
  • the steel sheets of Comparative Examples 1 to 7 in which at least one of the lengths of MnS at the position is out of the scope of the present invention, at least one of compressive strength, DWTT characteristics, and HIC resistance was inferior.
  • the steel plates of Comparative Examples 8 to 12 having the composition of Steels 11 to 15 as Comparative Examples were inferior in at least one of compressive strength, DWTT characteristics, and HIC resistance.
  • the obtained line pipe 1 was measured for tensile strength, yield strength, compressive strength, DWTT fracture surface ratio ( ⁇ 20 ° C.), CAR of HIC test, HAZ toughness, and WM (Weld Metal) toughness. Table 4 shows the measurement results.
  • the tensile strength, the DWTT fracture surface ratio ( ⁇ 20 ° C.), and the CAR of the HIC test were measured in the same manner as the above-described measurements on the steel sheet.
  • the yield strength, compressive strength, HAZ toughness, and WM toughness were measured as follows.
  • HAZ toughness A Charpy test piece with a V-notch was taken from a position 2 mm deep from the outer peripheral surface of the line pipe. The V notch of this test piece was provided so that the fracture surface after the Charpy impact test included HAZ and WM by 50% each by area ratio. Using the obtained V-notched Charpy test piece, a Charpy impact test was conducted in accordance with JIS Z2242 (2005) under a temperature condition of ⁇ 20 ° C., and Charpy absorbed energy (J) was defined as HAZ toughness (J). .
  • the line pipes 1 and 2 produced using the steel sheet of the present invention example were also excellent in compressive strength, DWTT characteristics, and HIC resistance, similarly to the steel sheet of the present invention example. Further, in the line pipes 1 and 2, good results were obtained with respect to HAZ toughness and WM toughness.

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PCT/JP2014/069471 2013-07-25 2014-07-23 ラインパイプ用鋼板及びラインパイプ WO2015012317A1 (ja)

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BR112015029358-1A BR112015029358B1 (pt) 2013-07-25 2014-07-23 placa de aço para tubo para condução e tubo para condução
RU2015151179A RU2623569C1 (ru) 2013-07-25 2014-07-23 Толстолистовая сталь для магистральной трубы и магистральная труба
JP2014551471A JP5748032B1 (ja) 2013-07-25 2014-07-23 ラインパイプ用鋼板及びラインパイプ
CN201480022395.3A CN105143489B (zh) 2013-07-25 2014-07-23 管线管用钢板和管线管
KR1020157031046A KR101709887B1 (ko) 2013-07-25 2014-07-23 라인 파이프용 강판 및 라인 파이프
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JP2020059887A (ja) * 2018-10-10 2020-04-16 日本製鉄株式会社 油井用電縫鋼管およびその製造方法
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US10801092B2 (en) 2015-12-21 2020-10-13 Posco Thick steel plate having excellent low-temperature toughness and hydrogen-induced cracking resistance, and method for manufacturing same
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EP3026140A1 (en) 2016-06-01
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JP5748032B1 (ja) 2015-07-15
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