WO2014010150A1 - 厚肉高強度耐サワーラインパイプおよびその製造方法 - Google Patents
厚肉高強度耐サワーラインパイプおよびその製造方法 Download PDFInfo
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/02—Rigid pipes of metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/06—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
- B21C37/08—Making tubes with welded or soldered seams
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
- C21D9/085—Cooling or quenching
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- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
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- G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
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- C21D2211/00—Microstructure comprising significant phases
- C21D2211/002—Bainite
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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Definitions
- the present invention relates to a heavy-wall high-strength sour-resistant pipe (line-pipe-for-sour-gas-service) and a method for producing the same, and preferably has a tube thickness of 20 mm or more and a tensile strength of 560 MPa or more. Related to things.
- Patent Documents 1 to 3 quantified the chemical component parameters quantifying the influence of alloy elements concentrated on the center segregation on the center segregation hardness and the formation of MnS in the center segregation and Ca clusters in the inclusion accumulation zone.
- Patent Documents 4 to 7 disclose a method of ensuring excellent HIC resistance performance by measuring the Mn concentration, Nb, and Ti concentration in the central segregation part and controlling the concentration below a certain level.
- the length of the non-crimped portion of the center segregation portion is controlled to a certain value or less to suppress the concentration of alloy elements in the center segregation portion and the accompanying increase in hardness, and to ensure excellent HIC resistance performance.
- a method is disclosed.
- Patent Document 9 the upper limit of the size of inclusions and NbTiCN combined with S, N, and O generated in the center segregation is regulated and controlled within the range by chemical components and slab heating conditions, thereby providing excellent resistance.
- a method for ensuring HIC performance is disclosed.
- Patent Document 10 discloses a method of ensuring excellent HIC resistance performance by reducing Nb to less than 0.01%, thereby suppressing generation of NbCN that becomes a HIC starting point in central segregation. .
- Patent Document 11 an excellent DWTT is obtained by setting the heating temperature at the time of slab reheating in a thick-walled high-strength line pipe to a condition in which NbCN in the slab is solid-solved and coarsening of austenite grains is suppressed as much as possible.
- a method for achieving both performance and HIC performance is disclosed.
- Patent Documents 12 and 13 in order to optimally control the form of Ca added to suppress MnS generation at the center segregation, the composition ratio of Ca—Al—O is optimized to form a fine sphere.
- a method for suppressing the generation of HIC starting from Ca clusters and coarse TiN and ensuring excellent HIC resistance is disclosed.
- Patent Document 14 regarding the determination of the lower limit of the accelerated cooling start temperature, the generation of a band-like structure is suppressed and excellent HIC resistance performance is ensured by considering C / Mn and the total amount of unrecrystallized zone reduction. A method is disclosed.
- Patent Documents 15 and 16 describe excellent HIC resistance performance by increasing the rolling end temperature in order to suppress the deterioration of the HIC propagation stop performance of the microstructure accompanying the flattening of crystal grains due to non-recrystallization zone rolling. A method of ensuring is disclosed.
- Patent Document 17 a structure form in which fine precipitates are dispersed in a ferrite structure through optimization of accelerated cooling and on-line rapid heating, reduction of surface hardness by surface ferrite formation and increase in strength by precipitation strengthening. And a method for ensuring excellent HIC resistance is disclosed.
- Patent Documents 18 to 20 disclose a method of achieving both strength and HIC performance by making the microstructure mainly bainite by the same method as Patent Document 17.
- Patent Documents 22 to 25 after accelerated cooling, rapid heating is performed by an induction heating device installed online, thereby adjusting the microstructure and hardness distribution in the thickness direction of the steel sheet to ensure excellent HIC resistance. A method is disclosed.
- Patent Document 22 describes that the generation of MA in the microstructure is suppressed and that the HIC propagation stop performance is enhanced as a uniform hardness distribution in the thickness direction, and Patent Document 23 describes high strength and HIC resistance.
- the component composition is a system in which segregation is suppressed and precipitation strengthening is possible, and a ferrite + bainite two-phase structure having a small hardness difference in the microstructure.
- the component composition is adjusted so that the concentration of the center segregation portion of each alloy element is lowered to reduce the hardness of the center segregation portion, and the metal structure in the steel plate surface layer portion is bainite or bainite + ferrite.
- the volume fraction of island martensite is described to be 2% or less.
- the cooling rate at the center of the plate thickness in the accelerated cooling is defined, and at the initial stage of cooling, the cooling rate is slowed down to lower the surface layer temperature to 500 ° C. or lower, and then the cooling rate is accelerated to ensure the strength.
- the method of implement achieving reduction of surface layer hardness and suppression of hardening of a center segregation part, and ensuring the outstanding HIC resistance performance is disclosed.
- Patent Documents 1 to 21 do not describe means for solving HIC generated on the surface layer of a thick high-strength sour line pipe.
- Patent Documents 22 to 25 are intended to prevent HIC generated from the vicinity of the surface layer hardened by accelerated cooling or the like, but the inclusions involved in the generation of HIC in the central segregation portion are in the vicinity of the surface layer portion. The influence of the above has not been studied at all, and there is a concern that it is insufficient as a method for suppressing HIC generated in the vicinity of the surface layer.
- an object of the present invention is to provide a thick high-strength sour line pipe having a tube thickness of 20 mm or more, which has excellent HIC resistance, and a manufacturing method thereof, which prevent HIC generated from the vicinity of the surface.
- the present inventors In order to obtain knowledge about the HIC resistance performance of a thick-walled, high-strength sour-line pipe manufactured as a low-O, ultra-low-S steel, the present inventors have a tube thickness of 20 mm or more in which a microstructure is formed into uniform bainite. The HIC generated at each position in the pipe thickness direction was examined for welded steel pipes, and the following findings were obtained.
- the suppression of HIC occurring in the center segregation area can be achieved by setting the center segregation hardness to 250 Hv10 or less and suppressing the generation of MnS. It is valid.
- the generation of MnS has a high correlation with the ACRM shown in the following equation, and the generation of MnS in the center segregation can be suppressed by setting the ACRM to 1.0 or more.
- ACRM (Ca ⁇ (1.23O ⁇ 0.000365)) / (1.25S), However, Ca, O, S content (mass%) 3.
- the HIC generated in the inclusion accumulation zone generated in the vertical bending type continuous casting machine can suppress the generation of Ca clusters and the generation of HIC when the ACRM is 4.0 or less.
- the occurrence of HIC in the vicinity of the surface layer cannot be organized only by the hardness of the surface layer, but the state of bubbles and inclusions generated in the vicinity of the surface layer is greatly affected. 5.
- the starting point of the HIC is a bubble or CaO cluster having a long diameter of 200 ⁇ m or more. Further, if the hardness in the vicinity of the surface layer exceeds 220 Hv10, HIC is generated starting from these bubbles and inclusions. If the long diameter of the bubbles and inclusions exceeds 1.5 mm, the hardness in the vicinity of the surface layer is set to 220 Hv10 or less. HIC occurs.
- the present invention targets a tube thickness of 20 mm or more, particularly 25 mm or more.
- the strain due to tube forming increases and HIC near the surface layer is more likely to occur.
- t / D exceeds 0.045, the HIC near the surface layer cannot be prevented due to the deterioration of the HIC performance due to strain near the surface layer and the increase in hardness. Therefore, the steel pipe with the t / D of 0.045 or less is targeted. .
- the present invention has been made by further studying the obtained knowledge, that is, the present invention, (1)
- the chemical composition of the steel pipe base material is, by mass, C: 0.020 to 0.060%, Si: 0.50% or less, Mn: 0.80 to 1.50%, P: 0.00.
- the hardness of the center segregation part is 250 Hv10 or less, the position from the inner surface in the tube thickness direction +1 mm to 3/16 of the tube thickness (T), and the position from the outer surface +1 mm to 13/16 of the tube thickness (T)
- a thick-walled, high-strength, sour-line pipe having a major axis of bubbles, inclusions and inclusion clusters of 1.5 mm or less.
- the chemical composition of the steel pipe base material part is by mass, Cu: 0.50% or less, Ni: 1.00% or less, Cr: 0.50% or less, Mo: 0.50% or less, V : Thick, high-strength sour line pipe according to (1), which contains one or more of 0.100% or less and Ti: 0.030% or less.
- the tube thickness is 20 mm or more, and T / D is 0.045 or less (T is the tube thickness (mm), D is the tube diameter (mm)), (1) or (2) Thick and high strength sour line pipe.
- a continuous cast slab having the chemical composition described in (1) or (2) is reheated to 1000 to 1150 ° C., and after hot rolling at a total reduction of 40 to 90% in the non-recrystallized region,
- the average cooling rate from 700 ° C. to 600 ° C. from the surface temperature of Ar3 ⁇ t ° C. or more (t is the plate thickness (mm)) to 350 to 550 ° C. is 3/16 position of the surface layer + 1 mm to the plate thickness in the plate thickness direction.
- a method for producing a thick-walled, high-strength sour line pipe characterized by welding to a welded steel pipe.
- the tube thickness is 20 mm or more, and T / D is 0.045 or less (T is the tube thickness (mm), D is the tube diameter (mm)), (4) or (5) Manufacturing method for thick and high strength sour line pipes.
- a sample is cut out from the steel pipe base material, and the pipe thickness is 200 mm 2 or more in the pipe circumferential direction and the pipe longitudinal direction.
- Ultrasonic flaw detection is performed using a probe of 20 MHz or more on the inner surface in the direction + 1 mm to the position 3/16 of the tube thickness and the outer surface +1 mm to the position 13/16 of the tube thickness.
- a method for judging the HIC resistance of a thick, high-strength sour line pipe characterized by checking the presence or absence of an instruction.
- a thick high-strength sour line pipe having a pipe thickness of 20 mm or more having excellent HIC resistance at each position in the pipe thickness direction and the manufacturing conditions thereof are obtained, which is extremely effective industrially.
- C 0.020 to 0.060%
- C is an element that concentrates in the center segregation and further promotes the segregation of other elements to the center segregation. Therefore, C is preferably reduced from the viewpoint of securing the HIC performance, and is limited to 0.060% or less.
- it since it is an element that is inexpensive and effective for increasing the strength, it contains 0.020% or more from the viewpoint of securing the strength of the base material. Preferably it is 0.025 to 0.055%.
- Si 0.50% or less Si is an element used for deoxidation, and is contained to reduce inclusions and contribute to high strength. If Si exceeds 0.50%, the HAZ toughness deteriorates remarkably and the weldability also deteriorates, so the upper limit is made 0.50%. More preferably, it is 0.40% or less, and still more preferably 0.05 to 0.40%.
- Mn 0.80 to 1.50% It is desirable to reduce Mn from the viewpoint of securing HIC performance because Mn is concentrating significantly on the center segregation and increases the hardness of the center segregation. If Mn exceeds 1.50%, the hardness of center segregation is high and HIC performance cannot be ensured even if other alloy elements are adjusted, so the upper limit is made 1.50%. On the other hand, Mn is inexpensive and contributes to high strength, and suppresses the formation of ferrite during cooling. In order to obtain the effect, addition of 0.80% or more is necessary. More preferably, it is 1.00 to 1.50%.
- P 0.008% or less P is concentrated as much as possible in the center segregation and is reduced as much as possible in order to significantly increase the hardness of the center segregation. However, since reducing P causes an increase in steelmaking cost, it is allowed up to 0.008%. More preferably, it is 0.006% or less.
- S 0.0015% or less S is concentrated as much as possible in the center segregation, forms MnS in the center segregation part, and significantly degrades the HIC performance, so it is reduced as much as possible.
- reducing S results in an increase in steelmaking cost, so 0.0015% is allowed. More preferably, it is 0.008% or less.
- Al 0.080% or less Al is an essential element for reducing inclusions by deoxidation.
- the content exceeds 0.08%, problems such as deterioration of HAZ toughness, deterioration of weldability and clogging of alumina in the immersion nozzle during continuous casting occur, so the upper limit is made 0.08%. More preferably, it is 0.05% or less.
- Nb 0.005 to 0.050%
- Nb expands the non-recrystallized region at the time of controlled rolling, and imparts to ensure the toughness of the base material. In order to obtain the effect, it is necessary to add at least 0.005% or more.
- Nb is concentrated in the center segregation, and coarse NbCN or NbTiCN is crystallized at the time of solidification to become the starting point of HIC and deteriorate the HIC performance, so the upper limit is made 0.05%. More preferably, it is 0.010 to 0.040%.
- Ca 0.0010 to 0.0040% Ca suppresses the production
- N 0.0080% or less N is an unavoidable impurity element, but if the content is 0.0080% or less, the base material toughness and HIC performance are not deteriorated, so the upper limit is made 0.0080%.
- O is an unavoidable impurity element, and may be reduced because the generation amount of Al 2 O 3 and CaO is increased to deteriorate the HIC performance below the surface layer and in the inclusion accumulation zone. preferable. However, reducing O results in an increase in steelmaking cost, so 0.0030% is allowed. More preferably, it is 0.0020% or less.
- Ceq (%) 0.320 or less Ceq (%) is an index representing the amount of alloying elements necessary to secure the base material strength of the thick-walled, high-strength sour line pipe, and is set to 0.320 or more.
- the upper limit is not particularly specified, but is preferably 0.400 or less from the viewpoint of weldability.
- PHIC (%) 0.960 or less PHIC (%) is a parameter indicating the degree of hardening of center segregation, and the larger the value, the higher the hardness of center segregation, which promotes the generation of HIC at the center of the tube thickness. If the PHIC (%) is 0.960 or less, the center segregation hardness can be 250 Hv10 or less, and excellent HIC resistance can be secured, so the upper limit is 0.960. More preferably, it is 0.940 or less. PHIC (%) is obtained by the following formula.
- PHIC (%) 4.46C + 2.37Mn / 6 + (1.74Cu + 1.7Ni) / 5 + (1.18Cr + 1.95Mo + 1.74V) /15+22.36P
- Each alloy element has a content (mass%) in the chemical component.
- ACRM (%) 1.00 to 4.00
- ACRM (%) is an index for quantifying the effect of controlling the morphology of MnS by Ca.
- ACRM (%) is 1.00 or more, the generation of MnS at the center segregation is suppressed, and the HIC at the tube thickness center. Is suppressed.
- the ACRM (%) exceeds 4.00, CaO clusters are likely to be generated and HIC is likely to occur, so the upper limit is set to 4.00. More preferably, it is 1.00 to 3.50.
- ACRM (%) is obtained by the following equation.
- ACRM (%) (Ca ⁇ (1.23O ⁇ 0.000365)) / (1.25S)
- Each alloy element has a content (mass%) in the chemical component.
- PCA (%) 4.00 or less
- PCA (%) is an index indicating the CaO cluster generation limit due to Ca.
- PCA (%) exceeds 4.00, CaO clusters are likely to be generated, and the vicinity of the surface layer and inclusions
- the upper limit is set to 4.00 because HIC easily occurs in the integrated band.
- PCA (%) is obtained by the following equation.
- PCA (%) 10000CaS 0.28
- Each alloy element has a content (mass%) in the chemical component.
- the above is the basic component composition of the thick and high strength sour line pipe according to the present invention, and the balance is Fe and inevitable impurities.
- the present invention one or more of the following alloy elements can be contained from the viewpoint of further improving the base material strength and the HAZ toughness.
- Cu 0.50% or less Cu is an element that contributes to increasing the strength of the base material, but it should also be kept from excessive inclusion because it is also an element that concentrates in central segregation. Further, if Cu is contained in an amount exceeding 0.50%, the weldability and the HAZ toughness are deteriorated. Therefore, when contained, the upper limit is made 0.50%.
- Ni 1.00% or less Ni is an element that contributes to increasing the strength of the base material. However, excessive concentration should be avoided because it is also an element that concentrates in central segregation. Further, if Ni is contained in excess of 1.00%, weldability is deteriorated, and since it is an expensive element, when it is contained, the upper limit is made 1.00%.
- Cr 0.50% or less Although Cr is an element that contributes to increasing the strength of the base material, excessive content should be avoided because it is also an element that concentrates in central segregation. Further, if Cr is contained in excess of 0.50%, the weldability and the HAZ toughness are deteriorated. Therefore, when it is contained, the upper limit is made 0.50%.
- Mo 0.50% or less Although Mo is an element that contributes to increasing the strength of the base material, excessive content should be refrained because it is also an element that concentrates in central segregation. Further, if Mo is contained in an amount exceeding 0.50%, the weldability and the HAZ toughness are deteriorated. Therefore, when contained, the upper limit is made 0.50%.
- V 0.100% or less V is an element that contributes to increasing the strength of the base material. However, V is also an element that concentrates in central segregation, so excessive content should be avoided. Further, if V is contained in excess of 0.100%, the weldability and the HAZ toughness are deteriorated. Therefore, when V is contained, the upper limit is made 0.100%.
- Ti 0.030% or less Ti has an effect of improving HAZ toughness as well as reducing solid solution N by forming TiN and suppressing deterioration of base metal toughness.
- Ti when Ti is excessively contained, the generation of NbTiCN is promoted by center segregation, and HIC is easily generated.
- the upper limit is made 0.030%.
- the microstructure of the steel pipe base material portion is 90% or more of bainite at a position of at least the inner surface +2 mm to the outer surface +2 mm in the tube thickness direction.
- the inner surface is the inner surface of the steel pipe, and the outer surface is the outer surface of the steel pipe.
- the structure of the steel pipe base material part is desirably a single-phase structure from the viewpoint of preventing the occurrence of HIC, and in order to obtain a desired strength as a thick-walled high-strength sour line pipe, it may be a bainite structure. Because it is necessary, a bainite single phase structure is adopted.
- the structure fraction (area ratio) of bainite is preferably 100%, but even if less than 10% of ferrite, cementite, and MA are included, it does not affect the prevention of HIC generation. Therefore, it is 90% or more. More preferably, it is 95% or more.
- the hardness of the region excluding the center segregation part is 220 Hv10 or less, and the hardness of the center segregation part is 250 Hv10 or less. Lower hardness is desirable. If the maximum diameter of inclusions and bubbles in the vicinity of the surface layer is 1.5 mm or less, it is possible to suppress the occurrence of HIC in the vicinity of the surface layer by setting the hardness in the vicinity of the surface layer to 220 Hv10 or less, more preferably 210 Hv10 or less. is there.
- the upper limit is set to 250 Hv10.
- the major axis of bubbles, inclusions, and inclusion clusters existing at positions from the inner surface in the tube thickness direction +1 mm to 3/16 of the tube thickness (T) and from the outer surface +1 mm to 13/16 of the tube thickness (T) 1.5 mm or less HIC in the vicinity of the surface layer is generated by the presence of one or more of bubbles, inclusions, and inclusion clusters (CaO clusters).
- the HIC performance is not deteriorated if the size of the CaO clusters and bubbles is 1.5 mm or less in the major axis dimension.
- a method for measuring inclusions either a microscopic observation of a cross section near the surface layer or a nondestructive inspection method may be used, but since it is necessary to measure a large volume, nondestructive such as ultrasonic flaw detection is required. By inspection is desirable.
- the measurement position is the same position as the HIC generation position in the vicinity of the surface layer (positions from the inner surface in the tube thickness direction + 1 mm to 3/16 of the tube thickness (T)) And an outer surface +1 mm to a position (up to 13/16 of the tube thickness (T)) in the tube circumferential direction and the tube longitudinal direction, at least an area of 200 mm 2 or more is performed using a probe of 20 MHz or more. Confirm that there is no instruction of 5mm or more.
- Total rolling reduction in non-recrystallized region 40-90%
- Rolling in the non-recrystallized region has the effect of flattening the microstructure and improving the base metal toughness.
- a reduction of 40% or more is necessary, so the lower limit is made 40%.
- the upper limit is made 90%. More preferably, it is 60 to 85%.
- Accelerated cooling starting temperature Ar3-t ° C or more at the surface temperature of the steel plate (t is the plate thickness (mm))
- the accelerated cooling start temperature is Ar3-t ° C. or higher (t is the plate thickness (mm)), more preferably Ar3-t / 2 ° C. or higher (t is the plate thickness (mm)).
- Accelerated cooling stop temperature 350-550 ° C at the surface temperature of the steel sheet Higher strength can be achieved as the stop temperature of accelerated cooling is lower.
- the cooling stop temperature is less than 350 ° C.
- the bainite lath is transformed into MA.
- HIC is easily generated by the martensitic transformation of the center segregation part.
- the temperature exceeds 550 ° C., a part of untransformed austenite is transformed into MA and HIC is easily generated, so the upper limit is set to 550 ° C.
- Average cooling rate of accelerated cooling 120 ° C./s or less near the surface layer, 20 ° C./s or more near the center of the plate thickness If the cooling rate of accelerated cooling near the surface layer is fast, the surface layer hardness increases and HIC is likely to occur. In order to make the surface layer hardness after pipe forming 220Hv10 or less, the cooling rate in the vicinity of the surface layer needs to be 120 ° C / s or less, so the upper limit is 120 ° C / s. In the vicinity of the surface layer, a position from the inner surface in the plate thickness direction +1 mm to 3/16 of the plate thickness (t) and a position from the outer surface +1 mm to 13/16 of the plate thickness (t) are set.
- the higher the cooling rate at the center of the plate thickness the higher the strength of the base material.
- the cooling rate at the center of the plate thickness is set to 20 ° C./s or more.
- the cooling rate near the surface layer may increase locally when a thick scale remains on the surface layer.
- the steel having the chemical composition shown in Table 1 was made into a slab by a continuous casting method, the slab was reheated under the conditions shown in Table 2, hot-rolled, accelerated cooled, and then air-cooled.
- the cooling rate at the center of the plate thickness for accelerated cooling was determined by heat conduction calculation from the temperature of the plate surface.
- the bainite fraction of the microstructure of the steel pipe base metal part was measured by preparing a sample that had been subjected to nital etching for the inner surface +2 mm position, the outer surface +2 mm position, and the center of the tube thickness, and was observed with an optical microscope. The value of the place with the lowest bainite fraction was adopted.
- the hardness of the steel pipe other than the central segregation part was measured at a 1 mm pitch from the inner surface +1 mm to the outer surface +1 mm using a Vickers hardness tester with a load of 10 kg, and the maximum value was used.
- the hardness of the center segregation part 20 points of the hardness of the center segregation part were measured by a micro Vickers hardness tester with a load of 50 g, and the maximum value was used.
- Bubbles and inclusions in the vicinity of the surface layer were measured by C-scan (probe 25 MHz).
- the measuring method is 10 mm thick from the inner surface of the steel pipe, cut out 5 rectangular samples of 100 mm in the longitudinal direction and 20 mm in the circumferential direction of the pipe, set so that the inner surface side becomes the bottom, position from the inner surface +1 mm to 3 / 16T
- the flaw detection gate was set to flaw detection. At that time, a dummy material with a 1.5 mm diameter hole with the same thickness as the sample was previously detected, and the sample was also measured under the conditions set so that the instruction by the hole would be 100% sensitivity, When an instruction exceeding 100% was issued, it was determined that there were inclusions or holes of 1.5 mm or more.
- the strength of the steel pipe was evaluated with an API full-thickness tensile test specimen collected from the pipe circumferential direction, and the steel pipe with a tensile strength of 560 MPa was regarded as acceptable.
- Two DWTT tests drop weight test
- the average shear shear surface ratio was 85% or more, and passed.
- three HIC tests were conducted for each solution A of NACE TM0284-2003, and a steel pipe with a maximum value of 10% or less in the CLR evaluation was regarded as acceptable (excellent HIC resistance performance).
- Table 3 shows the microstructure observation results, ultrasonic flaw detection results, and material test results of the welded steel pipe obtained. It was confirmed that all of the welded steel pipes within the scope of the present invention have excellent HIC resistance performance while satisfying the strength and DWTT performance required as a line pipe. On the other hand, among welded steel pipes whose component composition and / or manufacturing conditions are outside the scope of the present invention, those having a microstructure bainite fraction or hardness distribution outside the scope of the present invention are subject to CLR evaluation in the HIC test. It was inferior compared with.
Abstract
Description
2.また、MnSの発生は、下式に示すACRMとの相関が高く、ACRMを1.0以上にすることで、中心偏析におけるMnSの生成を抑制することができる。
ACRM=(Ca-(1.23O-0.000365))/(1.25S)、
但し、Ca、O、Sは含有量(質量%)
3.垂直曲げ型連続鋳造機で発生する介在物集積帯に発生するHICは、ACRMを4.0以下にするとCaクラスタの生成が抑制でき、HICの発生も抑制できる。
5.表層近傍に発生するHICの破面について調査した結果、HICの起点は長径で200μ以上の気泡あるいはCaOクラスタである。また、表層近傍の硬さが220Hv10を超えるとこれらの気泡や介在物を起点としたHICが発生し、気泡や介在物の長径が1.5mmを越えると表層近傍硬さを220Hv10以下にしてもHICが発生する。
7.aの場合、製鋼プロセスにおける気泡や粗大クラスタを鋼中で残存させないことにより達成可能である。しかし、粗大クラスタ(介在物)を残存させないためには、気泡を残存させて介在物を浮上促進させなければならず、製鋼プロセスにおける微妙なバランスを制御する必要があり、製造安定性が十分に確保できない可能性が非常に高い。
8.bの場合、鋼板製造プロセスにおいて表層硬さを低減し、造管後の表層近傍硬さを220Hv10以下に低減することができればHICの発生を抑制することが可能で、1.5mm以上の気泡や介在物を検知することは、比較的容易である。
また、管厚が厚くなるほど、外径が小さくなるほど、造管によるひずみが大きくなり表層近傍のHICが発生しやすくなる。t/Dが0.045を超えると、表層近傍のひずみによるHIC性能の劣化と硬さの上昇によって、表層近傍のHICを防げなくなるため、t/Dが0.045以下の鋼管を対象とする。
(1)鋼管母材部の化学成分が、質量%で、C:0.020~0.060%、Si:0.50%以下、Mn:0.80~1.50%、P:0.008%以下、S:0.0015%以下、Al:0.080%以下、Nb:0.005~0.050%、Ca:0.0010~0.0040%、N:0.0080%以下、O:0.0030%以下を含有し、式(1)によるCeqが0.320以上、式(2)によるPHICが0.960以下、式(3)によるACRMが1.00~4.00、式(4)によるPCAが4.00以下、残部Fe及び不可避的不純物で、管厚方向のミクロ組織が、内表面+2mm~外表面+2mmの領域で、90%以上のベイナイトを含み、管厚方向の硬さ分布において、中心偏析部を除く領域の硬さが220Hv10以下、中心偏析部の硬さが250Hv10以下で、管厚方向の内表面+1mm~管厚(T)の3/16までの位置および外表面+1mm~管厚(T)の13/16までの位置に存在する気泡や介在物および介在物クラスタの長径が1.5mm以下であることを特徴とする厚肉高強度耐サワーラインパイプ。
Ceq=C+Mn/6+(Cu+Ni)/15+(Cr+Mo+V)/5・・・式(1)
PHIC=4.46C+2.37Mn/6+(1.74Cu+1.7Ni)/5+(1.18Cr+1.95Mo+1.74V)/15+22.36P・・・式(2)
ACRM=(Ca-(1.23O-0.000365))/(1.25S)・・・式(3)
PCA=10000CaS0.28・・・式(4)
式(1)~(4)において、各合金元素は化学成分中の含有量(質量%)とする。
(2)鋼管母材部の化学成分が更に、質量%で、Cu:0.50%以下、Ni:1.00%以下、Cr:0.50%以下、Mo:0.50%以下、V:0.100%以下、Ti:0.030%以下の1種又は2種以上を含有することを特徴とする(1)に記載の厚肉高強度耐サワーラインパイプ。
(3)管厚が20mm以上で、T/Dが0.045以下(Tは管厚(mm)、Dは管径(mm))であることを特徴とする(1)または(2)記載の厚肉高強度耐サワーラインパイプ。
(5)熱間圧延後、加速冷却直前に鋼板表面での噴射流衝突圧が1MPa以上のデスケーリングを行なうことを特徴とする(4)記載の厚肉高強度耐サワーラインパイプの製造方法。
(7)(4)乃至(6)のいずれか一つに記載の製造方法で溶接鋼管とした後、鋼管母材からサンプルを切り出して、管周方向と管長手方向において200mm2以上、管厚方向の内表面+1mm~管厚の3/16までの位置および外表面+1mm~管厚の13/16までの位置を20MHz以上の探触子を用いて超音波探傷を行い、1.5mm以上の指示の有無を確認することを特徴とする厚肉高強度耐サワーラインパイプの耐HIC性能の判定方法。
[化学成分]以下の説明において%表示は、質量%とする。
C:0.020~0.060%
Cは、中心偏析に濃化し、さらに中心偏析への他の元素の偏析を助長する元素であるため、HIC性能確保の観点からは低減した方がよく、0.060%以下に制限する。一方、安価かつ高強度化に有効な元素であるため、母材強度を確保する観点から、0.020%以上を含有する。好ましくは0.025~0.055%である。
Siは、脱酸に用いる元素で、介在物を低減し、高強度化に寄与するため含有する。Siを0.50%を超えて含有すると、HAZ靭性が著しく劣化し、溶接性も劣化するため、上限を0.50%とする。より好ましくは、0.40%以下、さらに好ましくは、0.05~0.40%である。
Mnは、中心偏析に顕著に濃化して、中心偏析の硬さを上昇させるためHIC性能確保の観点から、低減することが望ましい。Mnが1.50%超えになると、他の合金元素の調整を行なっても中心偏析の硬さが高くHIC性能が確保できないため、上限を1.50%とする。一方で、Mnは、安価でかつ高強度化に寄与し、冷却中のフェライトの生成を抑制する。その効果を得るためには、0.80%以上の添加が必要である。より好ましくは、1.00~1.50%である。
Pは、中心偏析に顕著に濃化して、中心偏析の硬さを著しく増加させるためできるだけ低減する。しかしながら、Pを低減することは、製鋼コストの増大を招くため、0.008%まで許容する。より好ましくは、0.006%以下である。
Sは、中心偏析に顕著に濃化して、中心偏析部でMnSを形成し、HIC性能を顕著に劣化させるため、できるだけ低減する。しかしながら、Sを低減することは、製鋼コストの増大を招くため、0.0015%まで許容する。より好ましくは、0.008%以下である。
Alは脱酸により介在物を低減するために必須の元素である。一方で、0.08%を超えて含有するとHAZ靭性の劣化、溶接性の低下さらには連続鋳造時の浸漬ノズルのアルミナ詰りなどの問題が生じるため上限を0.08%とする。より好ましくは、0.05%以下である。
Nbは、固溶Nbとして存在すると制御圧延時の未再結晶域を拡大し、母材の靭性確保に付与する。その効果を得るためには少なくとも0.005%以上は添加する必要がある。一方で、Nbは中心偏析に濃化し、凝固時に粗大なNbCNあるいはNbTiCNを晶出しHICの起点となり、HIC性能を劣化させるため、上限を0.05%とする。より好ましくは、0.010~0.040%である。
Caは、中心偏析に生成するMnSの生成を抑制し、HIC性能を向上させる。その効果が得られるためには、少なくとも0.0010%は必要である。一方で、Caを過剰に添加すると、表層近傍や介在物集積帯でCaOクラスタが生成し、HIC性能を劣化させるため、上限を0.0040%とする。
Nは、不可避的不純物元素であるが、0.0080%以下の含有であれば、母材靭性やHIC性能を劣化させないため、上限を0.0080%とする。
Oは、不可避的不純物元素であり、Al2O3やCaOの生成量が増えることによって、表層下や介在物集積帯でのHIC性能を劣化させるため低減することが好ましい。しかしながら、Oを低減することは、製鋼コストの増大を招くため、0.0030%まで許容する。より好ましくは、0.0020%以下である。
Ceq(%)は、厚肉高強度耐サワーラインパイプの母材強度を確保するために必要な合金元素量を表す指標で、0.320以上とする。上限については、特に規定しないが、溶接性の観点から0.400以下とすることが好ましい。Ceq(%)は下式で求める。
Ceq(%)=C+Mn/6+(Cu+Ni)/15+(Cr+Mo+V)/5
各合金元素は化学成分中の含有量(質量%)とする。
PHIC(%)は、中心偏析の硬化度を示すパラメータで、この値が大きいほど中心偏析の硬さが高くなり、管厚中心でのHIC発生を助長する。PHIC(%)が0.960以下であれば、中心偏析の硬さを250Hv10以下とすることができ、優れた耐HIC性能を確保できるため、上限を0.960とする。より好ましくは、0.940以下である。PHIC(%)は下式で求める。
PHIC(%)=4.46C+2.37Mn/6+(1.74Cu+1.7Ni)/5+(1.18Cr+1.95Mo+1.74V)/15+22.36P
各合金元素は化学成分中の含有量(質量%)とする。
ACRM(%)は、CaによるMnSの形態制御の効果を定量化する指標で、ACRM(%)が1.00以上になると、中心偏析でのMnSの生成が抑制されて管厚中心でのHICの発生が抑制される。一方で、ACRM(%)が4.00を超えるとCaOクラスタが生成しやすくなり、HICが発生しやすくなるため、上限を4.00とする。より好ましくは、1.00~3.50である。ACRM(%)は下式で求める。
ACRM(%)=(Ca-(1.23O-0.000365))/(1.25S)
各合金元素は化学成分中の含有量(質量%)とする。
PCA(%)は、CaによるCaOクラスタ発生限界を示す指標で、PCA(%)が4.00を超えるとCaOクラスタが生成しやすくなり、表層近傍や介在物集積帯でのHICが発生しやすくなるため、上限を4.00とする。PCA(%)は下式で求める。
PCA(%)=10000CaS0.28
各合金元素は化学成分中の含有量(質量%)とする。
Cuは、母材の高強度化に寄与する元素であるが、中心偏析に濃化する元素でもあるので過度な含有は控えるべきである。また、Cuを0.50%を超えて含有すると、溶接性およびHAZ靭性の劣化を招くため、含有させる場合は、上限を0.50%とする。
Niは、母材の高強度化に寄与する元素であるが、中心偏析に濃化する元素でもあるので過度な含有は控えるべきである。また、Niを1.00%を超えて含有すると、溶接性の劣化を招き、また高価な元素であるため、含有させる場合は、上限を1.00%とする。
Crは、母材の高強度化に寄与する元素であるが、中心偏析に濃化する元素でもあるので過度な含有は控えるべきである。また、Crを0.50%を超えて含有すると、溶接性およびHAZ靭性の劣化を招くため、含有させる場合は、上限を0.50%とする。
Moは、母材の高強度化に寄与する元素であるが、中心偏析に濃化する元素でもあるので過度な含有は控えるべきである。また、Moを0.50%を超えて含有すると、溶接性およびHAZ靭性の劣化を招くため、含有させる場合は、上限を0.50%とする。
Vは、母材の高強度化に寄与する元素であるが、中心偏析に濃化する元素でもあるので過度な含有は控えるべきである。また、Vを0.100%を超えて含有すると、溶接性およびHAZ靭性の劣化を招くため、含有させる場合は、上限を0.100%とする。
Tiは、TiNを形成することにより固溶Nを減少させて母材靭性の劣化を抑制するだけでなく、HAZ靭性を向上させる効果がある。一方で、Tiを過剰に含有すると、中心偏析でNbTiCNの発生を助長し、HICを発生しやすくするため、含有する場合は、上限を0.030%とする。
鋼管母材部のミクロ組織は、管厚方向で少なくとも内表面+2mm~外表面+2mmの位置のミクロ組織を90%以上のベイナイトとする。内表面は鋼管内側の表面、外表面は鋼管外側の表面とする。
管厚方向の硬さ分布において、中心偏析部を除く領域の硬さが220Hv10以下、中心偏析部の硬さが250Hv10以下
厚肉高強度ラインパイプでは、表層近傍のHICが問題となるため、表層硬さは低い方が望ましい。表層近傍における介在物や気泡の最大径が1.5mm以下であれば、表層近傍の硬さを220Hv10以下、より好ましくは210Hv10以下にすることで表層近傍におけるHICの発生を抑制することが可能である。
[表層近傍の気泡や介在物]
管厚方向の内表面+1mm~管厚(T)の3/16までの位置および外表面+1mm~管厚(T)の13/16までの位置に存在する気泡や介在物および介在物クラスタの長径が1.5mm以下
表層近傍のHICは気泡や介在物および介在物クラスタ(CaOクラスタ)の一種または二種以上が存在することで発生する。表層近傍の硬さを220Hv10以下、より好ましくは210Hv10以下に低減した場合、CaOクラスタや気泡の大きさが、それらの長径寸法で1.5mm以下の場合、HIC性能を劣化させない。なお、介在物の測定方法としては、表層近傍の断面の顕微鏡観察によるもの、非破壊検査によるものいずれの方法によってもよいが、大きな体積について測定する必要があるため、超音波探傷などの非破壊検査によるものが望ましい。
本発明に係る厚肉高強度耐サワーラインパイプの好ましい製造方法について説明する。
スラブ加熱温度(slab heating temperature):1000~1150℃
スラブ加熱温度は、高いほど強度が上昇するが、靭性が劣化するため、所望の強度、靭性に応じて最適な範囲に設定する必要がある。スラブ加熱温度が1000℃未満になると、固溶Nbが確保できず、母材の強度、靭性ともに劣化するため、下限を1000℃とする。一方で、1150℃を超えると中心偏析に生成した粗大なNbCNがさらに凝集粗大化してHICの発生を容易とするため、上限を1150℃とする。
未再結晶域での圧延は、ミクロ組織を偏平化し、母材靭性を向上させる効果がある。その効果を得るためには、40%以上の圧下が必要であるため下限を40%とする。一方で、90%を超えて圧下すると母材靭性の向上効果がすでに飽和しているため大きく得られないことと、HICの伝播停止性能を劣化させるため、上限を90%とする。より好ましくは、60~85%である。
均一なベイナイト組織とするため、加速冷却開始温度をAr3-t℃以上(tは板厚(mm))、より好ましくは、Ar3-t/2℃以上(tは板厚(mm))とする。
加速冷却の停止温度は低いほど高強度化が可能となる。一方で、冷却停止温度が350℃未満になると、ベイナイトのラス間がMAに変態する。さらには、中心偏析部がマルテンサイト変態することによりHICの発生が容易となる。また、550℃を超えると未変態オーステナイトの一部がMAに変態し、HICが発生しやすくなるため、上限を550℃とする。
表層近傍の加速冷却の冷却速度が速いと表層硬さが上昇してHICが発生しやすくなる。造管後の表層硬さを220Hv10以下にするためには、表層近傍の冷却速度を120℃/s以下にする必要があるため、上限を120℃/sとする。表層近傍は、板厚方向の内表面+1mm~板厚(t)の3/16までの位置および外表面+1mm~板厚(t)の13/16までの位置とする。
Claims (7)
- 鋼管母材部の化学成分が、質量%で、C:0.020~0.060%、Si:0.50%以下、Mn:0.80~1.50%、P:0.008%以下、S:0.0015%以下、Al:0.080%以下、Nb:0.005~0.050%、Ca:0.0010~0.0040%、N:0.0080%以下、O:0.0030%以下を含有し、式(1)によるCeqが0.320以上、式(2)によるPHICが0.960以下、式(3)によるACRMが1.00~4.00、式(4)によるPCAが4.00以下、残部Fe及び不可避的不純物で、
管厚方向のミクロ組織が、内表面+2mm~外表面+2mmの領域で、90%以上のベイナイトを含み、
管厚方向の硬さ分布において、中心偏析部を除く領域の硬さが220Hv10以下、中心偏析部の硬さが250Hv10以下で、
管厚方向の内表面+1mm~管厚の3/16までの位置および外表面+1mm~管厚の13/16までの位置に存在する気泡や介在物および介在物クラスタの長径が1.5mm以下であることを特徴とする厚肉高強度耐サワーラインパイプ。
Ceq=C+Mn/6+(Cu+Ni)/15+(Cr+Mo+V)/5・・・式(1)
PHIC=4.46C+2.37Mn/6+(1.74Cu+1.7Ni)/5+(1.18Cr+1.95Mo+1.74V)/15+22.36P・・・式(2)
ACRM=(Ca-(1.23O-0.000365))/(1.25S)・・・式(3)
PCA=10000CaS0.28・・・式(4)
式(1)~(4)において、各合金元素は化学成分中の含有量(質量%)とする。 - 鋼管母材部の化学成分が更に、質量%で、Cu:0.50%以下、Ni:1.00%以下、Cr:0.50%以下、Mo:0.50%以下、V:0.100%以下、Ti:0.030%以下の1種又は2種以上を含有することを特徴とする請求項1に記載の厚肉高強度耐サワーラインパイプ。
- 管厚が20mm以上で、T/Dが0.045以下(Tは管厚(mm)、Dは管径(mm))であることを特徴とする請求項1または2記載の厚肉高強度耐サワーラインパイプ。
- 請求項1または2記載の化学成分を有する連続鋳造スラブを、1000~1150℃に再加熱し、未再結晶域での全圧下率が40~90%で熱間圧延後、表層温度がAr3-t℃以上(tは板厚(mm))より350~550℃まで、700℃~600℃の平均冷却速度が、板厚方向に表層+1mm~板厚の3/16位置および裏層+1mm~板厚の13/16位置において120℃/s以下、板厚中心において20℃/s以上で加速冷却した後、冷間加工によりパイプ状に曲げ加工し、両端部の突合せ部を溶接して溶接鋼管とすることを特徴とする厚肉高強度耐サワーラインパイプの製造方法。
- 熱間圧延後、加速冷却直前に鋼板表面での噴射流衝突圧が1MPa以上のデスケーリングを行なうことを特徴とする請求項4記載の厚肉高強度耐サワーラインパイプの製造方法。
- 管厚が20mm以上で、T/Dが0.045以下(Tは管厚(mm)、Dは管径(mm))であることを特徴とする請求項4または5記載の厚肉高強度耐サワーラインパイプの製造方法。
- 請求項4乃至6のいずれか一つに記載の製造方法で溶接鋼管とした後、鋼管母材からサンプルを切り出して、管周方向と管長手方向において200mm2以上、管厚方向の内表面+1mm~管厚の3/16までの位置および外表面+1mm~管厚の13/16までの位置を20MHz以上の探触子を用いて超音波探傷を行い、1.5mm以上の指示の有無を確認することを特徴とする厚肉高強度耐サワーラインパイプの耐HIC性能の判定方法。
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CN107326261A (zh) * | 2017-06-16 | 2017-11-07 | 武汉钢铁有限公司 | 低屈强比薄规格高强抗酸管线钢热轧卷板及其制造方法 |
WO2019064459A1 (ja) * | 2017-09-28 | 2019-04-04 | Jfeスチール株式会社 | 耐サワーラインパイプ用高強度鋼板およびその製造方法並びに耐サワーラインパイプ用高強度鋼板を用いた高強度鋼管 |
JP6521196B1 (ja) * | 2017-09-28 | 2019-05-29 | Jfeスチール株式会社 | 耐サワーラインパイプ用高強度鋼板およびその製造方法並びに耐サワーラインパイプ用高強度鋼板を用いた高強度鋼管 |
JP2020193375A (ja) * | 2019-05-29 | 2020-12-03 | Jfeスチール株式会社 | 耐サワーラインパイプ用溶接鋼管及びその製造方法 |
JP7226102B2 (ja) | 2019-05-29 | 2023-02-21 | Jfeスチール株式会社 | 耐サワーラインパイプ用溶接鋼管の製造方法 |
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CN106086646A (zh) | 2016-11-09 |
RU2621093C2 (ru) | 2017-05-31 |
JPWO2014010150A1 (ja) | 2016-06-20 |
KR20150029711A (ko) | 2015-03-18 |
US20150152982A1 (en) | 2015-06-04 |
CN106086646B (zh) | 2019-02-19 |
RU2015104050A (ru) | 2016-08-27 |
BR112015000515B1 (pt) | 2019-05-14 |
EP2871252A1 (en) | 2015-05-13 |
CN104428437A (zh) | 2015-03-18 |
KR20170083158A (ko) | 2017-07-17 |
BR112015000515A2 (pt) | 2017-06-27 |
EP2871252A4 (en) | 2016-03-02 |
IN2014KN02973A (ja) | 2015-05-08 |
KR101757710B1 (ko) | 2017-07-14 |
CN104428437B (zh) | 2017-03-08 |
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