WO2009061006A1 - ラインパイプ用鋼板及び鋼管 - Google Patents
ラインパイプ用鋼板及び鋼管 Download PDFInfo
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- WO2009061006A1 WO2009061006A1 PCT/JP2008/070726 JP2008070726W WO2009061006A1 WO 2009061006 A1 WO2009061006 A1 WO 2009061006A1 JP 2008070726 W JP2008070726 W JP 2008070726W WO 2009061006 A1 WO2009061006 A1 WO 2009061006A1
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- Prior art keywords
- less
- steel
- pipes
- hic
- hardness
- Prior art date
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 92
- 239000010959 steel Substances 0.000 title claims abstract description 92
- 239000013256 coordination polymer Substances 0.000 claims abstract description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 238000005204 segregation Methods 0.000 claims description 66
- 239000010949 copper Substances 0.000 claims description 46
- 229910052802 copper Inorganic materials 0.000 claims description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000003466 welding Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims 1
- 238000001816 cooling Methods 0.000 description 28
- 238000012360 testing method Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000005336 cracking Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000005098 hot rolling Methods 0.000 description 7
- 229910000734 martensite Inorganic materials 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005242 forging Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 210000003462 vein Anatomy 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910001563 bainite Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 235000019362 perlite Nutrition 0.000 description 2
- 239000010451 perlite Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002436 steel type Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002180 anti-stress Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012932 thermodynamic analysis Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
-
- 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
- C21D2211/004—Dispersions; Precipitations
Definitions
- the present invention is resistant to hydrogen-induced cracking (hereinafter referred to as HI C14 (Anti-Hydrogen Induced Cracking)) used in linepipe for transportation of crude oil and natural gas.
- HI C14 Anti-Hydrogen Induced Cracking
- High-strength steel plate for linepipe, and steel pipes for line pipes made using this steel sheet, and particularly severe HIC resistance is required.
- Pipe thickness This relates to steel pipes for line pipes suitable for line pipes with a thickness of 20 mm or more. Background art
- line pipes are made of copper plates manufactured by thick plate mills or hot rolling mills using UO E forming (U0E forming), press bend forming, roll forming, etc. It is molded and manufactured.
- Line pipes used to transport crude oil and natural gas containing hydrogen sulfide (hereinafter sometimes referred to as “line pipe for sour gas service”) have strength, toughness and weldability ( In addition to weldability, hydrogen-induced cracking resistance (HIC resistance) and stress-corrosion cracking resistance (SCC resistance (Anti-Stress Corrosion Cracking)) are required.
- HIC resistance hydrogen-induced cracking resistance
- SCC resistance Anti-Stress Corrosion Cracking
- HIC hydrogen-induced cracking
- Japanese Patent Application Laid-Open Nos. Sho 6 1-6 0 8 6 6 and No. Sho 6 1-1 6 5 2 0 7 disclose the reduction of elements that have a high segregation tendency (C, Mn, P, etc.)
- the generation of island martensite (MA const uent) that becomes the starting point of cracks in the center segregation aria, and the martensite (martensite) that becomes the propagation path of cracks (propagation path)
- Japanese Patent Laid-Open No. 5-255747 proposes a carbon equivalent formula based on a segregation coefficient and suppresses cracks in the central segregation part by making it equal to or less than a certain value. Has been proposed.
- Japanese Patent Laid-Open No. 2002-363689 discloses a method for regulating the segregation degree of Nb and Mn in the center segregation part to a certain level or less. A method has been proposed in which the size of inclusions starting from the HIC and the hardness of the central segregation part are specified.
- the method of reducing the carbonitride containing Nb to a very small size of 5 ⁇ m or less as disclosed in Japanese Patent Laid-Open No. 2006-63351 is effective in suppressing HIC generation at the center segregation part.
- coarse Nb carbonitrides crystallize in the final solidified part (crystallize).
- the generation of cracks based on Nb carbonitride that is generated at a certain frequency is suppressed as well as the generation of HIC. Therefore, it is necessary to manage the material of the center segregation part very strictly.
- the object of the present invention is to solve the above-mentioned problems of the prior art, and is required for a high-strength line pipe steel plate excellent in HIC resistance, particularly a sour line pipe having a pipe thickness of 20 mm or more.
- the purpose is to provide a high-strength sour line pipe steel plate with excellent HIC resistance that can sufficiently cope with severe HIC resistance.
- Another object of the present invention is to provide a steel pipe for a line pipe using a high-strength line pipe steel plate having such excellent performance.
- the steel pipes targeted by the present invention are all steel pipes with APIX 6 5 or more (yield stress is 65 ksi or more, 45 500 MPa or more), and high tensile strength of 5 35 MPa or more. It is a steel pipe. Disclosure of the invention
- the gist of the present invention is as follows.
- the steel plates and steel pipes for line pipes of the present invention have excellent HIC resistance, and can sufficiently meet the severe HIC resistance required especially for line pipes with a pipe thickness of 20 mm or more.
- Figure 1 Draft showing the relationship between the hardness of the core segregation part and the crack area rate in the HIC test for steel sheets with Mn S or Nb carbonitrides formed at the center segregation part.
- Figure 2 Graph showing the relationship between the CP value of steel sheet and the crack area ratio in the HIC test. BEST MODE FOR CARRYING OUT THE INVENTION
- Figure 1 shows an example of the results of an HIC test (test method is the same as in the examples described later) using a copper plate in which Mn S or Nb carbonitride is formed at the center segregation part.
- the present inventors have thermodynamically analyzed the concentration behavior of chemical components in the central segregation zone and derived the segregation coefficient for each alloy element.
- the segregation coefficient was derived according to the following procedure. First, voids due to solidification shrinkage or bulging are generated in the final solidified part during forging, and the surrounding molten steel flows into that part. Forms segregation spots that are concentrated. Next, the process of solidification of the concentrated segregation spot is the thermodynamic distribution coefficient (equilibrium distribution).
- the size of the Nb carbonitride which is the starting point of cracks in the HIC test, is suppressed to a certain value or less, and the metal structure is made to be a fine bainite-based structure.
- C is the most effective element for increasing the strength of the steel sheet produced by accelerated cooling. However, if the C content is less than 0.02%, sufficient strength cannot be secured. On the other hand, if it exceeds 0.06%, the toughness and HIC resistance deteriorate. Therefore, the C content is set to 0.02 to 0.06%.
- the Si amount is 0.5% or less. From the above viewpoint, the more preferable Si amount is 0.3% or less.
- Mn is added to improve the strength and toughness of copper, but if the amount of Mn is less than 0.8%, the effect is not sufficient, and if it exceeds 1.6%, the weldability and HIC resistance deteriorate. Therefore, the Mn content should be in the range of 0.8 to 1.6%. From the above viewpoint, the more preferable amount of Mn is 0.8 to 1.3%.
- P is an unavoidable impurity element and deteriorates the H IC resistance by increasing the hardness of the central segregation part. This tendency becomes prominent when it exceeds 0.08%. For this reason, Pi is set to not more than 0.0 0 8%. From the above viewpoint, the more preferable amount of P is 0.0 6% or less.
- S is generally an Mn S-based inclusion in copper, but its form is controlled from the Mn S-based to Ca-S inclusion by addition of Ca.
- the amount of S is large, the amount of C a S inclusions also increases, which can be the starting point of cracking in high strength materials. This tendency becomes prominent when the amount of S exceeds 0.0 0 0 8%. For this reason, the S amount is set to 0.0 0 0 8% or less.
- a 1 is added as a deoxidizer, but if the amount of A 1 exceeds 0.08%, the ductility deteriorates due to a decrease in cleanliness. For this reason, the amount of A1 is made 0.08% or less. More preferably, it is 0.06% or less.
- Nb is an element that suppresses grain growth during rolling, improves toughness by making fine grains, and enhances hardenability and strength after accelerated cooling.
- the amount of Nb is less than 0.05%, the effect is not sufficient.
- it exceeds 0.035% not only does the toughness of the welded heat affected zone deteriorate, Coarse Nb charcoal Nitride formation and HIC resistance deteriorates.
- the alloy elements are concentrated and the cooling rate is slow, so Nb carbonitrides are likely to crystallize in the central segregation zone.
- the size of the Nb carbonitride in the central segregation part is affected by the amount of Nb added, and by setting the upper limit of the amount of Nb to 0.035% or less, the size is reduced to 20 Aim or less. Is possible. Therefore, the Nb amount is set to 0.0 0 5 to 0.0 3 5%. Further, from the above viewpoint, the more preferable Nb amount is 0.010 to 0.030%.
- T i not only suppresses grain growth during slab heating by forming T i N, but also suppresses grain growth in the weld heat affected zone, and refines the base material and weld heat affected zone.
- the amount of Ding 1 is set to 0.005 to 0.025%.
- a more preferable Ti amount from the above viewpoint is 0.05 to 0.018%.
- C a is an element that controls the form of sulfide ⁇ inclusions and is effective for improving ductility and improving HIC resistance.
- the Ca content is less than 0.005%, the effect is not sufficient.
- the amount of Ca is set to 0.0 0 0 5 to 0.0 0 3 5%.
- the more preferable amount of Ca is from 0.0 0 10 to 0.0 30%.
- the steel sheet of the present invention can further contain one or more selected from Cu, Ni, Cr, Mo, and V in the following ranges.
- Cu 0.5% or less: Cu is an element effective in improving toughness and increasing strength, but in order to obtain the effect, 0.02% or more is preferable. If the Cu content exceeds 0.5%, weldability deteriorates. As a precaution, when Cu is added, it should be 0.5% or less. Further, from the above viewpoint, the more preferable amount of Cu is 0.3% or less.
- Ni is an element effective for improving toughness and increasing strength. In order to obtain the effect, Ni is preferably 0.02% or more. When the Ni content exceeds 1.0%, weldability deteriorates. Therefore, when adding Ni, the content should be 1.0% or less. Further, from the above viewpoint, the more preferable amount of Ni is 0.5% or less.
- Cr is an element effective for increasing the strength by increasing the hardenability, but in order to obtain the effect, it is preferably 0.02% or more. If the Cr content exceeds 0.5%, weldability deteriorates. Therefore, when adding Cr, the content should be 0.5% or less. Further, from the above viewpoint, the more preferable Cr amount is 0.3 ° / 0 or less. • Mo: 0.5% or less:
- Mo is an element effective for improving toughness and increasing strength. In order to obtain the effect, it is preferably 0.02% or more. If the Mo amount exceeds 0.5%, weldability deteriorates. Therefore, when adding Mo, the content should be 0.5% or less. Further, from the above viewpoint, the more preferable amount of Mo is 0.3% or less.
- V is an element that increases the strength without deteriorating the toughness.
- V is preferably 0.1% or more. If the V content exceeds 0.1%, the weldability is significantly impaired. Therefore, when adding V, the content should be 0.1% or less. Further, from the above viewpoint, the more preferable amount of V is 0.05% or less.
- the balance of the copper plate of the present invention is Fe and inevitable impurities.
- the CP value and C eq value represented by the following formulas are further defined.
- C (%), Mn (%), C r (%), Mo (%), V (%), Cu (%) Ni (%), and P (%) are the element content. Amount.
- the above formula for the CP value was devised to estimate the material of the central segregation part from the content of each alloy element.
- the lower the CP value the lower the hardness of the central prayer part.
- the value is preferably 0.92 or less.
- C eq is the carbon equivalent of the steel, and also the hardenability index.
- the purpose of the present invention is to improve the HIC performance of sour-resistant pipes, especially for thick materials with a pipe thickness of 20 mm or more.
- the C eq value is 0. It is necessary that more than 30 is necessary. For this reason, the C eq value is 0.30 or more. Higher C eq values give higher strength and allow for the production of thicker copper tubes. If the gold element concentration is too high, the hardness of the central segregation part will also increase and the HIC resistance will deteriorate.
- the steel sheet and steel pipe of the present invention preferably satisfy the following conditions with respect to the hardness of the center segregation part and the size of the Nb carbonitride from which H IC starts.
- the mechanism of crack growth in HIC is that hydrogen accumulates around the inclusions in the copper and cracks occur, and the cracks propagate around the inclusions. To grow into.
- the center segregation part is the most cracked, and is the place where the seed segregation occurs.
- the greater the hardness of the center segregation part the easier it is to crack.
- the hardness of the central segregation part is HV 2500 or less, crack propagation is unlikely to occur even if minute Nb carbonitride remains in the central segregation part. Can be suppressed.
- HV 2 500 the hardness of the central segregation part exceeds HV 2 500, cracks tend to propagate, and cracks generated in Nb carbonitride in particular tend to propagate.
- the hardness of the center segregation part is HV 2550 or less. If more stringent HIC performance is required, it is necessary to further reduce the hardness of the center segregation part. In that case, the hardness of the center segregation part is preferably HV 2 30 or less. .
- Nb carbonitrides generated in the central segregation part become the hydrogen accumulation site in the HIC test, and cracks occur starting from that.
- the larger the size of the Nb carbonitride the easier it is for cracks to propagate, and cracks propagate even if the hardness of the center segregation is HV 2500 or less.
- the length of the Nb carbonitride is 20 m or less, the propagation of cracks can be suppressed by setting the hardness of the center segregation part to HV 2550 or less.
- the length of Nb carbonitride is 20 ⁇ m or less, preferably 10 ⁇ m.
- the length of Nb carbonitride is the maximum length of the particle.
- the present invention is particularly suitable for a steel plate for a sour line pipe having a thickness of 20 mm or more.
- the plate thickness tube thickness
- the amount of alloying component added This is because the hardness of the central prayer part can be lowered and good HIC resistance can be easily obtained.
- the thicker the steel plate the more the alloy element needs to be added, making it difficult to reduce the hardness of the central prayer. Therefore, especially for thick copper plates with a thickness exceeding 25 mm, The effect can be exhibited more.
- the steel pipes targeted by the present invention are all steel pipes with APIX 6 5 or more (yield stress is 65 ksi or more, 45 500 MPa or more), and high tensile strength of 5 35 MPa or more. It is a steel pipe.
- the metal structure of the copper plate (and steel pipe) of the present invention desirably has a bainitic phase volume fraction of 75% or more, preferably 90% or more.
- the vanite phase is a metal structure with excellent strength and toughness. By setting its volume fraction to 75% or more, crack propagation is suppressed and high HIC resistance is obtained while maintaining high strength. Can do.
- a metal structure with a low volume fraction of the beanite phase for example, a mixed structure of a metal phase such as ferrite, perlite, MA (island martensite), or martensite, and a bainitic phase, is formed at the phase interface. Propagation of cracks is promoted and the HIC resistance is reduced.
- the volume fraction of the vein phase is 7 It is preferably 5% or more, and from the same viewpoint, the preferred volume fraction of the vinyl phase is 90% or more.
- the steel sheet of the present invention has a thick-walled structure by defining the chemical composition, the hardness of the central prayer part, and the size of the Nb carbonitride, and by making the metal structure a main body structure. Since excellent HIC resistance can be obtained even with materials, it can be manufactured basically by the same manufacturing method as the conventional method. However, in order to obtain not only HIC resistance but also optimum strength and toughness, it is desirable to manufacture under the conditions shown below.
- the slab heating temperature when hot rolling the slab is less than 100 ° C On the other hand, if it exceeds 1 2 0 0, the toughness deteriorates the DWT T property (Drop Weight Tear Test property). For this reason, the slab heating temperature is 1 0 0 0 ⁇
- the rolling end temperature is set to an appropriate temperature in consideration of necessary base material toughness and rolling efficiency. And, in order to obtain high base metal toughness it is preferable that the rolling reduction 6 0 0 / o or more on the pre-recrystallization temperature region (non- recrystall.ization temperature zone).
- accelerated cooling is preferably performed under the following conditions.
- the steel sheet temperature at the start of accelerated cooling is low, the amount of ferrite generated before accelerated cooling increases. In particular, if the temperature drop from the Ar 3 transformation point exceeds 10 ° C, the H IC resistance deteriorates. Also.
- the metal structure of the copper plate cannot secure a sufficient volume fraction bainitic phase (preferably 75% or more). For this reason, the steel plate temperature at the start of accelerated cooling is preferably (A r 3-10 ° C) or higher.
- the cooling rate in the accelerated cooling is preferably 5 / sec or more in order to stably obtain a sufficient strength.
- Accelerated cooling is an important process for obtaining high strength by the vein transformation.
- the steel plate temperature at the time of cooling stop of accelerated cooling exceeds 600, the bainitic transformation is incomplete and sufficient strength cannot be obtained.
- a hard structure such as MA (island martensite) is used.
- MA island martensite
- the steel plate temperature at the time of cooling stop at the time of accelerated cooling is set to 2 5 0 to 6 0 0 3 ⁇ 4: .
- the above-mentioned copper plate temperature is an average temperature in the plate thickness direction when there is a temperature distribution in the plate thickness direction of the copper plate, but if the temperature distribution in the plate thickness direction is relatively small, the copper plate
- the surface temperature may be the copper plate temperature.
- there is a temperature difference between the steel sheet surface and the interior immediately after accelerated cooling but the temperature difference is eliminated by heat conduction after a while, and a uniform temperature distribution in the sheet thickness direction is obtained.
- the copper plate temperature at the time of cooling stop of accelerated cooling may be obtained based on the surface temperature of the copper plate.
- the copper plate After accelerated cooling, the copper plate can be cooled as it is by air cooling, but it may be reheated in a gas combustion furnace or induction heating for the purpose of homogenizing the material inside the steel plate.
- the steel pipe for a line pipe is formed into a pipe shape by cold forming the steel sheet according to the present invention as described above, and the butted portion thereof. It is a steel pipe manufactured by seam welding.
- the method of cold forming is arbitrary, but it is usually formed into a tube shape by the U O E process or press bend.
- the seam welding of the butt portion is not limited as long as sufficient joint strength and joint toughness can be obtained, but submerged arc welding is particularly preferable from the viewpoint of welding quality and manufacturing efficiency.
- pipe expansion is performed to remove residual welding stress and improve the roundness of the steel pipe.
- the expansion ratio at this time is preferably 0.5 to 1.5% as a condition for obtaining a predetermined roundness of the steel pipe and removing the residual stress.
- Steel with the chemical composition shown in Table 1 was made into a slab by the continuous forging method. Were used to produce steel plates with thicknesses of 25.4 mm and 33 mm.
- the heated slab was rolled by hot rolling, and then accelerated cooling to a predetermined strength.
- the slab heating temperature was 1050 ° C
- the rolling end temperature was 840 to 80
- the start temperature of accelerated cooling was 800 to 7600.
- the stop temperature for accelerated cooling was set to 4500 to 5500 ° C.
- the strengths of the obtained copper plates all satisfy A P 1 X 65, and the tensile strength was 570 to 63 OMPa.
- a tensile test was conducted using a full thickness test piece in the rolling direction as a tensile test piece, and the tensile strength was measured.
- HIC test pieces were collected from a plurality of positions, and their HIC resistance characteristics were examined.
- the resistance to HIC is that the test specimen is immersed for 96 hours in 5% NaCl + 0.5% CH 3 COOH aqueous solution (normal NA CE solution) saturated with hydrogen sulfide with a pH of about 3. (Ultrasonic flaw detection) was used to investigate the presence or absence of cracks on the entire surface of the specimen, and the crack area rate (C AR) was evaluated.
- C AR crack area rate
- the hardness of the central segregation part is determined by polishing the cross sections in the thickness direction of multiple samples taken from the steel plate, and then lightly etching the portion where the segregation line is seen in the Vickers hardness tester with a load of 50 g (Vickers The maximum value was taken as the hardness of the central segregation part.
- the length of the Nb carbonitride in the central segregation part is determined by observing the fracture surface of the cracked part in the HIC test with an electron microscope, and Nb carbonitride on the fracture surface (fracture surf ace) The maximum grain length. If cracks do not occur in the HIC test, grind multiple sections of the HIC test piece and lightly etch, and the part where segregation lines can be seen is elemental mapping of Nb (elemental) using EPMA mapping) to identify Nb carbonitrides, and the maximum length of the grains was taken as the length of Nb carbonitrides.
- the center of the plate thickness and the t4 position are measured with an optical microscope.
- the area fraction of the vein phase was measured by image processing from the observed and photographed images, and the average value of the area fraction of the 3 to 5 visual fields was taken as the volume fraction.
- Table 2 shows the above test and measurement results.
- the steel sheets (steel types) 1 ⁇ 0 to 1 ⁇ and 1 ;, V, which are examples of the present invention, have a small crack area ratio by the H IC test and extremely good H IC resistance.
- the copper plate (copper type) L to 0, which is a comparative example has a CP value exceeding 0.95, so the hardness of the center segregation part is large, and a high crack area ratio is shown in the HIC test.
- the HIC resistance is inferior.
- steel plates (steel grades) P and Q have higher Mn or S content than the scope of the present invention, so Mn S- is generated in the central segregation part, and cracks originating from Mn S occur. Is inferior.
- the Nb content of steel plate (copper type) R is higher than the range of the present invention, coarse Nb carbonitrides are generated at the center segregation part, and the CP value is within the range of the present invention.
- HIC resistance is inferior.
- steel plate (copper type) S is Ca-free, and the shape of sulfide inclusions is not controlled by Ca, so HIC resistance is poor.
- the amount of Ca in steel sheet (steel type) T is higher than the range of the present invention, the amount of Ca-based oxides in copper increases and cracks start from these, resulting in poor HIC resistance.
- Steel pipes were manufactured using some of the steel sheets shown in Table 2. That is, a copper plate is cold-formed by a UOE process to form a pipe shape, and the butt portion is subjected to submerged arc welding (seam welding) on each of the inner and outer surfaces. % Pipe expansion processing was performed to produce a steel pipe with an external diameter of 7 1 1 mm. The manufactured steel pipe was subjected to the same HIC test as the steel sheet described above. The results are shown in Table 3. The HIC resistance is measured by cutting the length of one specimen into four equal parts, observing the cross section, and crack length rate (CLR) (total crack length). The test piece width (average value of 20 mm) was evaluated.
- CLR crack length rate
- a thick material having a thickness of 20 mm or more has extremely excellent anti-HIC performance, and can be applied to line pipes that require more stringent anti-HIC performance in recent years. It becomes possible to do.
- the present invention is effective when applied to a steel plate having a thickness of 20 mm or more. As the thickness becomes thicker, it is difficult to reduce the hardness of the central segregation portion because the addition of an alloy element is required. The effect can be achieved even with thick copper plates exceeding 25 mm.
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Abstract
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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CN200880115297A CN101855378A (zh) | 2007-11-07 | 2008-11-07 | 管道钢管用钢板及钢管 |
US12/741,271 US8801874B2 (en) | 2007-11-07 | 2008-11-07 | Steel plate and steel pipe for line pipes |
RU2010122959/02A RU2481415C2 (ru) | 2007-11-07 | 2008-11-07 | Стальной лист и стальная труба для трубопроводов |
EP08846950A EP2224028B1 (en) | 2007-11-07 | 2008-11-07 | Steel plate for line pipes and steel pipes |
KR1020107009878A KR101247089B1 (ko) | 2007-11-07 | 2008-11-07 | 라인 파이프용 강판 및 강관 |
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US (1) | US8801874B2 (ja) |
EP (1) | EP2224028B1 (ja) |
JP (1) | JP5343519B2 (ja) |
KR (1) | KR101247089B1 (ja) |
CN (1) | CN101855378A (ja) |
RU (1) | RU2481415C2 (ja) |
TW (1) | TWI392748B (ja) |
WO (1) | WO2009061006A1 (ja) |
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JP2009133005A (ja) | 2009-06-18 |
RU2010122959A (ru) | 2011-12-20 |
RU2481415C2 (ru) | 2013-05-10 |
US8801874B2 (en) | 2014-08-12 |
JP5343519B2 (ja) | 2013-11-13 |
KR20100070364A (ko) | 2010-06-25 |
KR101247089B1 (ko) | 2013-03-25 |
EP2224028A4 (en) | 2011-07-27 |
TW200930820A (en) | 2009-07-16 |
TWI392748B (zh) | 2013-04-11 |
US20100326559A1 (en) | 2010-12-30 |
EP2224028B1 (en) | 2012-08-29 |
CN101855378A (zh) | 2010-10-06 |
EP2224028A1 (en) | 2010-09-01 |
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