WO2013047702A1 - ラインパイプ用ホットコイル及びその製造方法 - Google Patents
ラインパイプ用ホットコイル及びその製造方法 Download PDFInfo
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- WO2013047702A1 WO2013047702A1 PCT/JP2012/074969 JP2012074969W WO2013047702A1 WO 2013047702 A1 WO2013047702 A1 WO 2013047702A1 JP 2012074969 W JP2012074969 W JP 2012074969W WO 2013047702 A1 WO2013047702 A1 WO 2013047702A1
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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 hot coil for a line pipe and a method for producing the same, and more particularly to a hot coil suitable for use in a line pipe for transporting natural gas and crude oil and a method for producing the hot coil.
- high-strength line pipes are increasing in order to 1) improve transportation efficiency by increasing pressure and 2) improve site construction efficiency by reducing the outer diameter and weight of line pipes.
- high-strength line pipes up to American Petroleum Institute (API) standard X120 (tensile strength of 915 MPa or more) are in practical use.
- API American Petroleum Institute
- These high-strength line pipes are generally manufactured by the UOE method, the bending roll method, the JCOE method, or the like.
- line pipes for long-distance transportation line pipes equivalent to API standard X60-70 are still widely used.
- a line pipe corresponding to X60 to 70 a spiral steel pipe or an ERW steel pipe having a high local construction efficiency is often used.
- a hot rolled steel sheet that is not wound in a coil shape As a material used for manufacturing a line pipe, when a line pipe is manufactured by a UOE method, a bending roll method, and a JCOE method, a hot rolled steel sheet that is not wound in a coil shape is used. On the other hand, when manufacturing a spiral steel pipe or an ERW steel pipe, a hot-rolled steel sheet wound in a coil shape is used.
- a hot-rolled steel sheet not wound in a coil shape is referred to as a thick plate
- a hot-rolled steel sheet wound in a coil shape is referred to as a hot coil.
- Patent Documents 1 to 10 describe hot coils used for manufacturing spiral steel pipes or ERW steel pipes.
- Patent Documents 11 to 14 describe thick plates used when manufacturing line pipes by the UOE method, bending roll method, and JCOE method.
- Line pipes for transporting combustibles such as crude oil and natural gas are required not only for reliability at room temperature but also for cold regions, so reliability at low temperatures is also required. Accordingly, the thick plate and hot coil, which are materials for the line pipe, are required to reduce variation in normal temperature strength and to improve low-temperature toughness.
- the thick plates described in Patent Documents 11 to 14 do not have a winding process, the degree of freedom in conditions for cooling the hot-rolled steel sheet is large, and a stable and uniform steel structure can be obtained. In addition, since there is no winding process, a desired steel structure can be stably obtained because sufficient time can be taken to keep the steel sheet in the recrystallization temperature range between rough rolling and finish rolling. As a result, the room temperature strength variations of the thick plates described in Patent Documents 11 to 14 are small, and the low temperature toughness is also excellent.
- Patent Documents 1 to 10 describe that the method of cooling the hot-rolled steel sheet is improved in order to reduce hot coil strength variation and improve low-temperature toughness.
- Patent Documents 1 and 2 and 6 to 9 describe that the steel sheet after hot rolling is cooled in multiple stages.
- there is a winding process in manufacturing a hot coil and rough rolling and finish rolling are continuously performed, which increases the restrictions on manufacturing conditions. Therefore, it has been difficult to obtain a hot coil that does not have a desired steel structure, has a small variation in normal temperature strength, and is excellent in low-temperature toughness only by improving the cooling method described in Patent Documents 1 to 10.
- An object of the present invention is to provide a hot coil for a line pipe and a method for manufacturing the same, in which a variation in room temperature strength is reduced and a low temperature toughness is improved even in a hot coil in which manufacturing conditions are often limited by a winding process.
- the normal temperature strength means tensile strength (TS), yield strength, yield ratio, and hardness at normal temperature.
- the present inventors have conducted intensive research and obtained the following knowledge. a) In order to reduce the variation in room temperature strength, it is necessary to make the base structure uniform in the plate thickness direction and the longitudinal direction after making the effective crystal grain size of the steel plate constituting the hot coil 10 ⁇ m or less. That is, it is not sufficient to make the base structure of the steel plate constituting the hot coil uniform in the thickness direction and the longitudinal direction as in the prior art. b) When the effective grain size of the steel structure is 10 ⁇ m or less, and the total of bainite and acicular ferrite is set to a predetermined area ratio or more as the base structure, the low temperature toughness is also improved.
- the present invention has been made on the basis of the above findings, and the gist thereof is as follows. (1) In mass%, C: 0.03-0.10%, Si: 0.01 to 0.50%, Mn: 0.5 to 2.5%, P: 0.001 to 0.03%, S: 0.0001 to 0.0030%, Nb: 0.0001 to 0.2%, Al: 0.0001 to 0.05%, Ti: 0.0001 to 0.030% and B: 0.0001 to 0.0005%
- the balance is the composition of iron and inevitable impurities, and the steel structure at the center of the plate thickness has an effective crystal grain size of 2 to 10 ⁇ m, and the total area ratio of bainite and acicular ferrite is 60 to 99%.
- the absolute value of AB is 0 to 30%
- the plate thickness is 7 A hot coil for a line pipe, characterized in that it has a tensile strength TS in the width direction of 400 to 700 MPa.
- the hot coil is further in mass%, Cu: 0.01 to 0.5%, Ni: 0.01 to 1.0%, Cr: 0.01 to 1.0%, Mo: 0.01 to 1.0%, V: 0.001 to 0.10%, W: 0.0001 to 0.5%, Zr: 0.0001 to 0.050% Ta: 0.0001 to 0.050% Mg: 0.0001 to 0.010%, Ca: 0.0001 to 0.005%, REM: 0.0001 to 0.005%, Y: 0.0001 to 0.005%, Hf: 0.0001 to 0.005% and Re: 0.0001 to 0.005% 1 type or 2 types or more are contained,
- the hot coil for line pipes as described in said (1) characterized by the above-mentioned.
- the hot-rolled steel sheet is retained for 100 to 500 seconds at least once between each rolling pass in the recrystallization temperature range for 0 to 500 seconds, and the obtained hot-rolled steel sheet is cooled separately in the first and second stages.
- the hot rolled steel sheet in the former stage cooling, is cooled by 0.5 to 15 ° C./second at the center of the thickness of the hot rolled steel sheet until the surface temperature of the hot rolled steel sheet reaches 600 ° C. from the cooling start temperature of the former stage.
- a method for producing a hot coil for a line pipe characterized in that cooling is performed at a speed and cooling is performed at a sheet thickness central portion of a hot-rolled steel sheet at a cooling rate faster than the preceding stage.
- the steel slab is further in mass%, Cu: 0.01 to 0.5%, Ni: 0.01 to 1.0%, Cr: 0.01 to 1.0%, Mo: 0.01 to 1.0%, V: 0.001 to 0.10%, W: 0.0001 to 0.5%, Zr: 0.0001 to 0.050% Ta: 0.0001 to 0.050% Mg: 0.0001 to 0.010%, Ca: 0.0001 to 0.005%, REM: 0.0001 to 0.005%, Y: 0.0001 to 0.005%, Hf: 0.0001 to 0.005% and Re: 0.0001 to 0.005% 1 or 2 types or more are contained,
- the manufacturing method of the hot coil for line pipes as described in said (3) characterized by the above-mentioned.
- the cooling of the preceding stage is started from a temperature range of 800 to 850 ° C., and the temperature range of 800 to 600 ° C. is cooled at a cooling rate of 0.5 to 10 ° C./second at the center of the plate thickness.
- the cooling in the preceding stage is started from a temperature range of 800 to 850 ° C., and the temperature range of 800 to 600 ° C. is cooled at a cooling rate of 0.5 to 10 ° C./second at the center of the plate thickness.
- the method for producing a hot coil for a line pipe according to (5) which is characterized in that
- the effective crystal grain size is set to a predetermined value or less, and the specific base structure is made uniform at the surface and the center of the plate thickness, thereby reducing the variation in room temperature strength and excellent in low temperature toughness.
- a hot coil can be provided.
- it is a hot coil that needs to be wound by both retaining the steel sheet during hot rolling between each rolling pass in the recrystallization temperature range and cooling the steel sheet after hot rolling in two stages. Even if it exists, the manufacturing method of the hot coil for line pipes which has the small dispersion
- FIG. 1 is a graph showing the relationship between the sum of bainite and acicular ferrite and the Charpy impact absorption energy at ⁇ 20 ° C. of a hot coil having a plate thickness of 16 mm.
- FIG. 2 is a diagram showing the influence of the cooling method on the variation in the sheet thickness direction of the steel sheet hardness.
- the effective crystal grain size of the steel structure at the center of the plate thickness is in the range of 2 to 10 ⁇ m. If the effective crystal grain size of the steel structure at the center of the plate thickness exceeds 10 ⁇ m, the effect of crystal grain refinement cannot be obtained, and desired characteristics cannot be obtained regardless of the base structure.
- the thickness is preferably 7 ⁇ m or less.
- the effective crystal grain size of the steel structure at the center of the plate thickness is less than 2 ⁇ m, the crystal grain refinement effect is saturated. Preferably it is 3 ⁇ m or more.
- the effective grain size of the steel structure was defined as the equivalent circle diameter of the region surrounded by the boundary having a crystal orientation difference of 15 ° or more using EBSP (Electron Back Scattering Pattern).
- Step structure in the center of the plate thickness 60 to 99% of the total area ratio of bainite and acicular ferrite
- the effective crystal grain size is set to 2 to 10 ⁇ m, and the area ratio of bainite and acicular ferrite at the center of the plate thickness is used as the base structure. It is necessary to make it 60 to 99% in total.
- the Charpy absorbed energy at ⁇ 20 ° C. of the hot coil is less than 150 J and the DWTT (Drop Weight Tear Test) ductile fracture surface ratio at 0 ° C. is 85.
- FIG. 1 is a diagram showing the relationship between the total area ratio of bainite and acicular ferrite and the Charpy impact absorption energy at ⁇ 20 ° C. in a hot coil having a plate thickness of 16 mm. As is clear from FIG. 1, the Charpy impact absorption energy at ⁇ 20 ° C. rapidly decreases when the total area ratio of bainite and acicular ferrite is less than 60%.
- the area of bainite and acicular ferrite The total rate is preferably 80% or more.
- the hot coil can contain inevitable steel structures such as cementite and pearlite, the total area ratio of bainite and acicular ferrite is 99. % Is the upper limit.
- bainite has a structure in which carbides are precipitated between laths or massive ferrites, or a structure in which carbides are precipitated in the laths.
- a structure in which carbides are not precipitated between the laths or in the laths is martensite and is distinguished from bainite.
- the absolute value of AB is 0 to 30%
- the base structure generally varies in the plate thickness direction and the longitudinal direction. In order to improve the reliability of the line pipe, it is necessary to make the base structures in the thickness direction and the longitudinal direction of the hot coil used for manufacturing the line pipe uniform. In other words, it is necessary to reduce the difference between the base tissues at any two sites.
- the absolute value of AB is defined.
- the absolute value of AB exceeds 30%, it means that the base structure of the linepipe hot coil varies greatly in the plate thickness direction and the longitudinal direction. If this variation is large, the room temperature strength of the hot coil for the line pipe varies, and as a result, the reliability of the plate thickness line pipe decreases. Therefore, the absolute value of AB is 30% or less. Preferably it is 20% or less. On the other hand, the lower limit of the absolute value of AB is 0%. An absolute value AB of 0% indicates no variation.
- the absolute value of AB is in the range of 0 to 30% even in the conventional hot coil manufacturing method.
- the absolute value of AB cannot be in the above range unless the manufacturing method of the present invention described later. This is particularly noticeable when the plate thickness is 10 mm or more.
- the plate thickness of the hot coil of the present invention is in the range of 7 to 25 mm. The range of 10 to 25 mm is preferable.
- the hot coil for a line pipe of the present invention is a material for producing a line pipe corresponding to API standard X60 to 70, which is most frequently used as a main line pipe for long-distance transportation. Therefore, the tensile strength TS in the width direction needs to be 400 to 700 MPa so as to satisfy API standards X60 to 70.
- the hot coil for a line pipe of the present invention can be obtained by hot rolling a steel slab having a predetermined component composition.
- the method for producing the steel slab may be a continuous casting method or a steel ingot method.
- the component composition will be described later.
- Step reheating temperature 1000-1250 ° C
- the time required for the recrystallization temperature range is shortened during hot rolling, and the steel sheet during hot rolling cannot be sufficiently recrystallized.
- austenite grains become coarse. Therefore, the heating temperature of the steel slab is in the range of 1000 to 1250 ° C.
- the reduction ratio in the recrystallization temperature range is less than 1.9, the effective crystallization of the steel structure can be achieved no matter how long the steel sheet during hot rolling is retained between the rolling passes in the recrystallization temperature range.
- the particle size cannot be 10 ⁇ m or less.
- it is 2.5 or more. This is because the residence time of the steel sheet during hot rolling between the rolling passes in the recrystallization temperature range can be shortened.
- the degree of recrystallization after rolling is saturated.
- it is 3.6 or less. This is because even if the reduction ratio is 3.6, recrystallization to the extent that there is no practical problem can be obtained.
- Step retention during hot rolling 100 to 500 seconds at least once between each rolling pass in the recrystallization temperature range
- the plate thickness after finish rolling that is, the plate thickness of the hot coil is less than 7 mm
- no retentive time is provided in rough rolling, and even if finish rolling is continuously performed, recrystallization is promoted and non-recrystallized.
- the reduction in the area can also be secured.
- the effective crystal grain size of the steel structure can be made 10 ⁇ m or less.
- the hot coil of the present invention if the plate thickness is 7 mm or more, it is sufficient that the steel plate during hot rolling is not retained for 100 seconds or more at least once between each rolling pass in the recrystallization temperature range. Austenite cannot be recrystallized. Moreover, the rolling reduction in finish rolling cannot be taken sufficiently. Therefore, in order to manufacture a hot coil having a thickness of 7 to 25 mm, which is the object of the present invention, the steel sheet is retained for 100 seconds or more between rolling passes at least once during the rough rolling in the recrystallization temperature range.
- the temperature range to make it stay is less than 1000 degreeC. This is because if it is retained at 1000 ° C. or higher, grain growth after recrystallization increases and low temperature toughness deteriorates. Then, after the stay, the remaining pass of rough rolling is performed, and then finish rolling is performed, so that the amount of reduction in the non-recrystallized region can be sufficiently secured. As a result, the effective crystal grain size of the steel sheet after winding, that is, the effective crystal grain size of the hot coil for line pipe can be made 10 ⁇ m or less.
- the residence time per time is 500 seconds or less. Preferably it is 400 seconds or less.
- the residence time in the rolling pass in which the steel sheet during hot rolling is not retained is 0 seconds.
- the total area ratio of bainite and acicular ferrite which are base structures, can be made uniform in the thickness direction and the longitudinal direction by the manufacturing method described below. That is, the absolute value of AB can be in the range of 0 to 30% when the sum of the area ratios of bainite and acicular ferrite at two arbitrary sites is A and B, respectively.
- the base structure varies in the thickness direction and the longitudinal direction, and as a result, the hardness of the hot coil wound with the steel sheet varies in the thickness direction and the longitudinal direction. In particular, the variation in the thickness direction is large.
- the aqueous medium boils. The form of boiling is nucleate boiling when the surface temperature of the steel sheet is high, and film boiling when the surface temperature of the steel sheet is low.
- the aqueous medium boils in either nucleate boiling or film boiling form, the steel sheet is stably cooled.
- the steel plate can be cooled uniformly if it instantaneously changes from nucleate boiling to film boiling.
- the steel sheet is cooled through a temperature range in which transition boiling occurs in which both nucleate boiling and film boiling are mixed.
- the transition boiling temperature range is passed in a short time so that the steel sheet is not cooled for a long time in the state of transition boiling, and the cooling of the steel sheet after hot rolling is divided into two stages, the first stage and the second stage.
- FIG. 2 is a diagram showing the influence of the cooling method on the variation in the thickness direction of the steel sheet hardness.
- the hardness in the vicinity of the surface layer of the steel sheet increases, and the hardness does not become constant in the sheet thickness direction. Arise.
- the hardness in the plate thickness direction becomes constant and no variation occurs. It can be seen that the two-stage cooling is effective for reducing the variation in the thickness direction of the base structure because the variation in hardness is caused by the variation in the base structure. Such a phenomenon also occurs in the longitudinal direction of the steel plate.
- the cooling rate of the first stage is 0.5 to 15 ° C./second at the center of the thickness of the hot-rolled steel sheet until the surface temperature of the hot-rolled steel sheet reaches 600 ° C. from the cooling start temperature of the previous stage.
- the aqueous medium nucleates and transition boiling does not occur. Accordingly, it is not necessary to particularly shorten the cooling time of the hot-rolled steel sheet in this temperature range, and therefore it is not necessary to set the cooling rate at the center part of the sheet thickness to more than 10 ° C / second.
- the cooling rate exceeds 15 ° C./second, it is advantageous to set the cooling rate to 15 ° C./second or less from the viewpoint of martensite transformation and the formation of bainite being suppressed. Preferably, it is 8 ° C./second or less.
- the cooling rate is less than 0.5 ° C./second, it takes too much time until the surface temperature of the hot-rolled steel sheet reaches 600 ° C., thereby impairing productivity. Therefore, the cooling rate of the central portion of the plate thickness needs to be 0.5 ° C./second or more. Preferably, it is 3 ° C./second or more.
- the cooling rate of 0.5 to 15 ° C./second is the cooling rate at the center of the thickness of the hot-rolled steel sheet, but 1.0 to 30 ° C./second when converted to the surface cooling rate of the hot-rolled steel sheet.
- the cooling rate of the latter stage needs to be faster than the former stage at the center of the thickness of the hot rolled steel sheet.
- the hot-rolled steel sheet having a surface temperature of less than 600 ° C. due to the preceding cooling is used for the subsequent cooling. If the cooling rate of the latter stage is slower than that of the former stage at the center of the thickness of the hot-rolled steel sheet, transition boiling occurs from the nucleate boiling to the film boiling when the transition proceeds from the former stage to the latter stage. As a result, the steel sheet cannot be cooled uniformly, and the base structure of the hot-rolled steel sheet varies in the thickness direction and the longitudinal direction. This is because transition boiling tends to occur when the surface of the hot-rolled steel sheet is 450 to 600 ° C.
- a preferable subsequent cooling rate is in the range of 40 to 80 ° C./second on the steel sheet surface.
- the range is more preferably 50 to 80 ° C./second, and further preferably 60 to 80 ° C./second.
- the ranges are 10 to 40 ° C./sec, 15 to 40 ° C./sec, and 20 to 40 ° C./sec, respectively.
- the aqueous medium is supplied to the surface of the steel plate from both the gravitational direction and the antigravity direction.
- the supply amount of the aqueous medium in the gravitational direction and the antigravity direction has the following relationship: Satisfied.
- Qg / Qc 1-10
- Qg Aqueous medium supply amount in the gravity direction (m 3 / sec)
- Qc Aqueous medium supply amount in anti-gravity direction (m 3 / sec)
- the hot coil for line pipe of the present invention may be manufactured under the following conditions.
- the rolling ratio in the non-recrystallization temperature region is preferably 2.5 to 4.0. This is because if the reduction ratio in the non-recrystallization temperature region is 2.5 or more, the effective crystal grain size can be further reduced to 10 ⁇ m or less. On the other hand, even if it exceeds 4.0, there is no change in the effective crystal grain size.
- Cooling in the first stage is started at 800 to 850 ° C., and the cooling rate in the first stage is 0.5 to 10 ° C./second at the center of the plate thickness in the temperature range where the surface temperature of the hot-rolled steel sheet is 800 ° C. to 600 ° C. It is preferable that This is because by setting the cooling start temperature in the previous stage to 800 to 850 ° C., ferrite can be generated, the yield ratio of the steel sheet is lowered, and the deformability is improved.
- the coiling temperature after cooling in the latter stage is preferably set to 450 to 600 ° C. This is because the total area ratio of bainite and acicular ferrite can be further increased, and the low-temperature toughness can be further improved.
- C (C: 0.03-0.10%) C is an element indispensable as a basic element for improving the strength of the base metal in steel. Therefore, addition of 0.03% or more is necessary. On the other hand, excessive addition exceeding 0.10% causes a decrease in weldability and toughness of the steel material, so the upper limit is made 0.10%.
- Si 0.01-0.50%
- Si is an element necessary as a deoxidizing element at the time of steel making, and it is necessary to add 0.01% or more to the steel.
- the upper limit is made 0.50%.
- Mn is an element necessary for ensuring the strength and toughness of the base material.
- Mn exceeds 2.5%, the toughness of the HAZ is remarkably lowered when a steel plate is welded to produce a line pipe.
- Mn is in the range of 0.5 to 2.5%.
- P is an element that affects the toughness of steel.
- P exceeds 0.03%, not only the base material but also the toughness of HAZ is remarkably lowered when the steel plate is welded to form a line pipe. Therefore, the upper limit is made 0.03%.
- P is an impurity element, it is preferable to reduce the content as much as possible, but the lower limit is set to 0.001% from the viewpoint of refining costs.
- Nb 0.0001 to 0.2%
- carbide and nitride are formed in the steel and the strength is improved.
- the toughness is reduced. Therefore, Nb is set in the range of 0.0001 to 0.2%.
- Al 0.0001 to 0.05%
- Al is usually added as a deoxidizer. However, if added over 0.05%, Ti-based oxides are not generated, so the upper limit is made 0.05%. On the other hand, since a certain amount is necessary for reducing the amount of oxygen in the molten steel, the lower limit is made 0.0001%.
- Ti 0.0001 to 0.030%
- Ti is added in an amount of 0.0001% or more as a deoxidizing material and further as a nitride forming element, crystal grains are refined.
- the upper limit is made 0.030%. Therefore, Ti is set in the range of 0.0001 to 0.030%.
- the characteristics of the hot coil for line pipe can be further improved by arbitrarily adding one or more of the following elements.
- Cu is an element effective for increasing the strength without decreasing the toughness. To increase the strength, it is preferable to add 0.01% or more. On the other hand, if it exceeds 0.5%, cracking is likely to occur when the steel piece is heated or welded. Therefore, Cu is preferably in the range of 0.01 to 0.5%.
- Ni 0.01-1.0%
- Ni is an element effective for improving toughness and strength, and in order to obtain the effect, addition of 0.01% or more is preferable.
- addition exceeding 1.0% lowers the weldability when producing a line pipe, so the upper limit is preferably made 1.0%.
- the upper limit is preferably set to 1.0%.
- Mo 0.01-1.0%
- Mo improves hardenability and at the same time forms carbonitride and improves strength.
- addition of 0.01% or more is preferable.
- the upper limit is preferably made 1.0%.
- V (V: 0.001 to 0.10%) V forms carbides and nitrides and is effective in improving strength. Addition of 0.001% or more is preferable for improving the strength. On the other hand, if it exceeds 0.10%, the toughness is reduced, so the upper limit is preferably made 1.0%.
- W has an effect of improving hardenability and simultaneously forming carbonitride to improve strength.
- W is preferably added in an amount of 0.0001% or more.
- the upper limit is preferably set to 0.5%.
- Zr and Ta like Nb, form carbides and nitrides and are effective in improving strength. In order to improve the strength, it is preferable to add 0.0001% or more of Zr and Ta, respectively. On the other hand, if each of Zr and Ta is added in excess of 0.050%, the toughness is reduced, so the upper limit is preferably made 0.050% or less.
- Mg 0.0001-0.010%
- Mg is added as a deoxidizing material, but if added over 0.010%, a coarse oxide is likely to be generated, and when producing a line pipe, when the steel plate is welded, the base material and HAZ toughness is reduced.
- addition of less than 0.0001% makes it difficult to produce oxides necessary for intragranular transformation and pinning particles. Therefore, Mg is preferably in the range of 0.0001 to 0.010%.
- Ca, REM, Y, Hf, and Re suppress the generation of elongated MnS by generating sulfides, and improve the characteristics in the thickness direction of the steel material, particularly the lamellar resistance.
- Ca, REM, Y, Hf, and Re are each added in an amount of less than 0.0001%, this improvement effect cannot be obtained.
- a steel piece having a thickness of 240 mm having the composition shown in Tables 1 and 2 was heated to a range of 1100 to 1210 ° C., and then roughly rolled to a plate thickness in the range of 70 to 100 mm, Hot rolling was performed in the crystallization temperature range. Then, as finish rolling, hot rolling was performed in a non-recrystallization temperature range of 750 to 880 ° C. to a thickness of 3 to 25 mm. Thereafter, the former cooling process was started when the surface temperature of the steel sheet was in the range of 750 to 850 ° C., and the latter cooling process was started when the surface temperature of the steel sheet was in the range of 550 to 700 ° C.
- Tables 3 to 4 show the detailed manufacturing conditions.
- the transfer thickness in Tables 3 to 4 is the thickness of the steel sheet when the rough rolling is completed and transferred to finish rolling.
- the steel structure and mechanical properties of the hot coil thus obtained were investigated.
- the base structure measured the total area ratio of bainite and acicular ferrite every 2 mm in the plate thickness direction and every 5000 mm in the longitudinal direction in addition to the center portion of the plate thickness. Then, ten arbitrary two sets were selected from each measurement site, the absolute values of AB were calculated for each set, and the minimum and maximum absolute values in the calculated 10 sets were obtained.
- the effective crystal grain size was measured by the method using EBSP described above at the center of the plate thickness of the hot coil. Further, at the base tissue measurement position, the Vickers hardness Hv was also measured, and the maximum value and the minimum value were obtained in the same manner as the base tissue, and the difference was regarded as variation.
- the invention examples of hot coil Nos. 1 to 17 and 30 to 47 all have an area ratio of bainite and acicular ferrite even if the plate thickness is 7 to 25 mm.
- the total and effective crystal grain size are within a predetermined range.
- the tensile strength (TS) is 400 to 700 MPa, and the variation thereof is 60 MPa or less.
- the variation in Vickers hardness is 20 Hv or less.
- the Charpy impact absorption energy at ⁇ 20 ° C. was 150 J or more
- the DWTT ductile fracture surface ratio at 0 ° C. was 85% or more.
- the Charpy impact absorption energy at ⁇ 40 ° C. is 200 J or more
- the DWTT ductile fracture surface ratio at ⁇ 20 ° C. is 85% or more.
- hot coil No. In Comparative Examples 18 to 29, since the total area ratio of bainite and acicular ferrite and at least one of the effective crystal grain sizes are out of the predetermined range, the desired strength or the like is not obtained. Variation is large. This is because rough rolling conditions or cooling conditions are outside a predetermined range. In addition, since the composition of the hot coils No. 48 to 63 was outside the predetermined range, at least one of the total area ratio of bainite and acicular ferrite and the effective crystal grain size was out of the predetermined range. As a result, it was confirmed that desired strength or the like was not obtained or that variations in strength or the like were large.
- the line pipe hot coil of the present invention has a small variation in room temperature strength and is excellent in low temperature toughness. Therefore, if a line pipe is manufactured using the line pipe hot coil of the present invention, a highly reliable line pipe can be obtained not only at room temperature but also at a low temperature. Therefore, the present invention has high industrial utility value.
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Abstract
Description
a)常温強度のばらつきを低減するには、ホットコイルを構成する鋼板の有効結晶粒径を10μm以下にした上で、基地組織を板厚方向と長手方向で均一にする必要がある。即ち、従来のように、ホットコイルを構成する鋼板の基地組織を板厚方向と長手方向で均一にするだけでは不十分であること。
b)鋼組織の有効結晶粒径を10μm以下にした上で、基地組織としてベイナイトとアシキュラーフェライトの合計を面積率で所定以上とすると、低温靭性も向上すること。
c)鋼組織の有効結晶粒径を10μm以下とするには、熱間圧延における粗圧延で十分に再結晶させておく必要がある。そのためには、巻き取り工程のあるホットコイルの製造においては、再結晶温度域での各圧延パス間で少なくとも1回、熱間圧延中の鋼板を所定時間滞留させる必要があること。
d)基地組織を板厚方向と長手方向で均一にするには、熱間圧延後の鋼板の冷却を多段にする必要があること。
e)常温強度のばらつきを低減するには、鋼組織の有効結晶粒径を所定以下とするとともに、基地組織を板厚方向と長手方向で均一にすることとが必要である。したがって、従来のように、2段冷却をするだけでは不十分で、2段冷却することと、再結晶温度域での各圧延パス間で熱間圧延中の鋼板を滞留させることの両方が必要であること。
(1)質量%で、
C :0.03~0.10%、
Si:0.01~0.50%、
Mn:0.5~2.5%、
P :0.001~0.03%、
S :0.0001~0.0030%、
Nb:0.0001~0.2%、
Al:0.0001~0.05%、
Ti:0.0001~0.030%及び
B :0.0001~0.0005%
を含有し、残部は鉄及び不可避的不純物の成分組成になり、板厚中心部の鋼組織が、有効結晶粒径で2~10μm、ベイナイト及びアシキュラーフェライトの面積率の合計で60~99%であるとともに、任意の2部位におけるベイナイト及びアシキュラーフェライトの面積率の合計を、それぞれ、A及びBとしたとき、A-Bの絶対値が0~30%であり、かつ、板厚が7~25mmであり、幅方向の引張強度TSが400~700MPaであることを特徴とするラインパイプ用ホットコイル。
Cu:0.01~0.5%、
Ni:0.01~1.0%、
Cr:0.01~1.0%、
Mo:0.01~1.0%、
V :0.001~0.10%、
W :0.0001~0.5%、
Zr:0.0001~0.050%
Ta:0.0001~0.050%
Mg:0.0001~0.010%、
Ca:0.0001~0.005%、
REM:0.0001~0.005%、
Y :0.0001~0.005%、
Hf:0.0001~0.005%及び
Re:0.0001~0.005%
のうち1種又は2種以上を含有することを特徴とする前記(1)に記載のラインパイプ用ホットコイル。
C :0.03~0.10%、
Si:0.01~0.50%、
Mn:0.5~2.5%、
P :0.001~0.03%、
S :0.0001~0.0030%、
Nb:0.0001~0.2%、
Al:0.0001~0.05%、
Ti:0.0001~0.030%及び
B :0.0001~0.0005%
を含有し、残部は鉄及び不可避的不純物の成分組成になる鋼片を、1000~1250℃に加熱した後、熱間圧延するに際し、再結晶温度域での圧下比を1.9~4.0、かつ、再結晶温度域での各圧延パス間で少なくとも1回、熱間圧延中の鋼板を100~500秒間滞留させて、得られた熱間圧延鋼板を、前段と後段に分けて冷却するにあたり、前段の冷却では、前記熱間圧延鋼板の表面温度が、前段の冷却開始温度から600℃となるまで、熱間圧延鋼板の板厚中心部で0.5~15℃/秒の冷却速度で冷却し、後段の冷却では、熱間圧延鋼板の板厚中心部で前段よりも速い冷却速度で冷却することを特徴とするラインパイプ用ホットコイルの製造方法。
Cu:0.01~0.5%、
Ni:0.01~1.0%、
Cr:0.01~1.0%、
Mo:0.01~1.0%、
V :0.001~0.10%、
W :0.0001~0.5%、
Zr:0.0001~0.050%
Ta:0.0001~0.050%
Mg:0.0001~0.010%、
Ca:0.0001~0.005%、
REM:0.0001~0.005%、
Y :0.0001~0.005%、
Hf:0.0001~0.005%及び
Re:0.0001~0.005%
のうち1種又は2種以上を含有することを特徴とする前記(3)に記載のラインパイプ用ホットコイルの製造方法。
本発明のラインパイプ用ホットコイルが、所望の特性を得るためには、先ず、板厚中心部の鋼組織の有効結晶粒径が2~10μmの範囲であることが必要である。板厚中心部の鋼組織の有効結晶粒径が10μmを超えると、結晶粒の微細化効果が得られず、基地組織をどのようにしても所望の特性を得ることができない。好ましくは7μm以下とする。一方、板厚中心部の鋼組織の有効結晶粒径を2μm未満としても、結晶粒の微細化効果は飽和する。好ましくは3μm以上とする。なお、鋼組織の有効結晶粒径は、EBSP(Electron Back Scattering Pattern)を用いて、15°以上の結晶方位差を有する境界で囲まれた領域の円相当径で定義した。
上述したように、ラインパイプ用ホットコイルが所望の特性を得るためには、有効結晶粒径を2~10μmとした上で、基地組織として、板厚中心部のベイナイト及びアシキュラーフェライトの面積率の合計で60~99%とする必要がある。ベイナイト及びアシキュラーフェライトの面積率の合計が60%未満であると、ホットコイルの-20℃でのシャルピー吸収エネルギーが150J未満、0℃でのDWTT(Drop Weight Tear Test)延性破面率が85%未満となり、ラインパイプを製造したときに必要な低温靭性を確保できない。図1は、板厚が16mmであるホットコイルにおける、ベイナイト及びアシキュラーフェライトの面積率の合計と-20℃でのシャルピー衝撃吸収エネルギーとの関係を示す図である。図1から明らかなように、-20℃でのシャルピー衝撃吸収エネルギーは、ベイナイト及びアシキュラーフェライトの面積率の合計が60%未満になると、急激に低下する。
ラインパイプ用ホットコイルは、板厚方向と長手方向で基地組織がばらつくのが一般的である。ラインパイプの信頼性を向上させるには、ラインパイプの製造に使用されるホットコイルの板厚方向と長手方向の基地組織を均一にする必要がある。即ち、任意の2部位における基地組織の差を小さくする必要がある。ここで、任意の2部位におけるベイナイト及びアシキュラーフェライトの面積率の合計を、それぞれ、A及びBとしたとき、A-Bの絶対値を定義する。A-Bの絶対値が30%を超えると、ラインパイプ用ホットコイルの基地組織が、板厚方向と長手方向で大きくばらついていることを意味する。このばらつきが大きいと、ラインパイプ用ホットコイルの常温強度がばらつき、その結果、板厚ラインパイプの信頼性が低下する。したがって、A-Bの絶対値は30%以下とする。好ましくは20%以下である。一方、A-Bの絶対値の下限は0%とする。A-Bの絶対値が0%とは、ばらつきがないことを示す。
板厚が7mm未満であると、従来のホットコイルの製造方法でも、A-Bの絶対値が0~30%の範囲となる。しかし、板厚が7mm以上であると、後述する本発明の製造方法でなければ、A-Bの絶対値を上記範囲とすることはできない。特に、板厚が10mm以上の場合、顕著である。一方、板厚が25mmを超えると、巻き取ることができない。したがって、本発明のホットコイルの板厚は7~25mmの範囲とする。好ましくは10~25mmの範囲である。
本発明のラインパイプ用ホットコイルは、長距離輸送用の幹線ラインパイプとして最も多く使用されている、API規格X60~70相当のラインパイプを製造するための素材である。したがって、API規格X60~70を満足するよう、幅方向の引張強度TSを400~700MPaとする必要がある。
鋼片の再加熱温度が1000℃未満であると、熱間圧延時に、再結晶温度域となる時間が短くなり、熱間圧延中の鋼板を十分に再結晶させることができない。一方、1250℃を超えると、オーステナイト粒が粗大化する。したがって、鋼片の加熱温度は、1000~1250℃の範囲とする。
再結晶温度域での圧下比が1.9未満であると、再結晶温度域での各圧延パス間で、熱間圧延中の鋼板を、いくら長時間滞留させても、鋼組織の有効結晶粒径を10μm以下にすることはできない。好ましくは2.5以上とする。再結晶温度域での各圧延パス間における熱間圧延中の鋼板の滞留時間を短くできるからである。一方、4.0を超えても圧延後の再結晶の程度は飽和する。好ましくは3.6以下とする。圧下比が3.6でも、実用上問題のない程度の再結晶が得られるからである。
仕上圧延後の板厚、即ち、ホットコイルの板厚が7mm未満の場合には、粗圧延で滞留時間を設けず、連続して仕上圧延を行っても、再結晶を促進させ、未再結晶域での圧下も確保できる。その結果、鋼組織の有効結晶粒径を10μm以下にすることができる。
Qg/Qc=1~10
ただし、Qg:重力方向の水媒体供給量(m3/秒)
Qc:反重力方向の水媒体供給量(m3/秒)
Cは、鋼における母材強度を向上させる基本的な元素として欠かせない元素である。したがって、0.03%以上の添加が必要である。一方、0.10%を超える過剰な添加は、鋼材の溶接性や靱性の低下を招くので、上限を0.10%とする。
Siは製鋼の際の脱酸元素として必要な元素であり、鋼中に0.01%以上の添加が必要である。一方、0.50%を超えると、ラインパイプを製造するために鋼板を溶接したとき、HAZの靱性が低下するため、上限を0.50%とする。
Mnは、母材の強度及び靱性の確保に必要な元素である。Mnが2.5%を超えると、ラインパイプを製造するために鋼板を溶接したとき、HAZの靱性が著しく低下する。一方、0.5%未満では、鋼板の強度確保が困難になる。したがって、Mnは0.5~2.5%の範囲とする。
Pは、鋼の靱性に影響を与える元素である。Pが0.03%を超えると、鋼板を溶接してラインパイプとしたときに、母材だけでなく、HAZの靱性を著しく低下させる。したがって、上限を0.03%とする。一方、Pは不純物元素であるので、含有量を極力低下させることが好ましいが、精錬コストの関係から、下限を0.001%とする。
Sは、0.0030%を超えて過剰に添加されると、粗大な硫化物の生成の原因となり、靱性を低減させるため、上限を0.0030%とする。一方、Sは不純物元素であるので、含有量を極力低下させることが好ましいが、精錬コストの関係から、下限を0.0001%とする。
Nbは、0.0001%以上添加することにより、鋼中で、炭化物及び窒化物を形成し、強度を向上させる。一方、0.2%を超えて添加すると、靱性の低下を招く。したがって、Nbは、0.0001~0.2%の範囲とする。
Alは、脱酸材として添加されるのが通常である。しかし、0.05%を超えて添加されると、Ti主体の酸化物が生成されないため、上限を0.05%とする。一方、溶鋼中の酸素量低減のため、一定量が必要であることから、下限を0.0001%とする。
Tiは、脱酸材として、さらには窒化物形成元素として、0.0001%以上添加することで、結晶粒を微細化する。しかし、過剰な添加は炭化物の形成による靱性の著しい低下をもたらすため、上限を0.030%とする。したがって、Tiは、0.0001~0.030%の範囲とする。
Bは、固溶すると焼入れ性を大きく増加させて、フェライトの生成を著しく抑制させる。したがって、上限を0.0005%とする。一方、下限は、精錬コストの関係から0.0001%とする。
Cuは、靱性を低下させることなく強度を上昇させるのに有効な元素である。強度の上昇には、0.01%以上添加することが好ましい。一方、0.5%を超えると、鋼片の加熱時や溶接時に、割れが生じやすくする。したがって、Cuは、0.01~0.5%の範囲とすることが好ましい。
Niは、靱性及び強度の改善に有効な元素であり、その効果を得るためには0.01%以上の添加が好ましい。一方、1.0%を超える添加は、ラインパイプを製造するときの溶接性が低下するため、上限を1.0%とすることが好ましい。
Crは、析出強化により、鋼の強度を向上させるため、0.01%以上の添加が好ましい。一方、過剰に添加すると、焼入れ性が過度に上昇し、かつ、ベイナイトを過剰に生成させるため、靱性が低下する。したがって、上限を1.0%とすることが好ましい。
Moは、焼入れ性を向上させると同時に、炭窒化物を形成し、強度を向上させる。強度の向上には、0.01%以上の添加が好ましい。一方、1.0%を超えると、靭性の著しい低下を招くから、上限を1.0%とすることが好ましい。
Vは、炭化物及び窒化物を形成し、強度の向上に効果がある。強度の向上には0.001%以上の添加が好ましい。一方、0.10%を超えると、靱性の低下を招くから、上限を1.0%とすることが好ましい。
Wは、焼入れ性を向上させると同時に、炭窒化物を形成し強度を改善する効果を有し、その効果を得るためには、0.0001%以上の添加が好ましい。一方、0.5%を超える過剰な添加は、靱性の著しい低下を招くため、上限を0.5%とすることが好ましい。
(Ta:0.0001~0.050%)
Zr及びTaは、Nbと同様に、炭化物及び窒化物を形成し、強度の向上に効果がある。強度の向上には、Zr及びTaを、それぞれ、0.0001%以上添加することが好ましい。一方、Zr及びTaを、それぞれ、0.050%を超えて添加すると、靱性の低下を招くため、上限を0.050%以下とすることが好ましい。
Mgは、脱酸材として添加されるが、0.010%を超えて添加されると、粗大な酸化物が生成し易くなり、ラインパイプを製造するため、鋼板を溶接したとき、母材及びHAZの靱性が低下する。一方、0.0001%未満の添加では、粒内変態及びピニング粒子として必要な酸化物の生成がされにくい。したがって、Mgは、0.0001~0.010%の範囲とすることが好ましい。
(REM:0.0001~0.005%)
(Y:0.0001~0.005%)
(Hf:0.0001~0.005%)
(Re:0.0001~0.005%)
Ca、REM、Y、Hf、及びReは、硫化物を生成することにより、伸長MnSの生成を抑制し、鋼材の板厚方向の特性、特に、耐ラメラティアー性を改善する。Ca、REM、Y、Hf、及びReは、それぞれ、0.0001%未満の添加では、この改善効果が得られない。一方、それぞれの添加が0.005%を超えると、Ca、REM、Y、Hf、及びReの酸化物個数が増加し、Mg含有を含有する微細酸化物の個数が減少する。したがって、これらは、それぞれ、0.0001~0.005%の範囲とすることが好ましい。なお、ここでいうREMは、Y、Hf、及びRe以外の希土類元素の総称とする。
Claims (11)
- 質量%で、
C :0.03~0.10%、
Si:0.01~0.50%、
Mn:0.5~2.5%、
P :0.001~0.03%、
S :0.0001~0.0030%、
Nb:0.0001~0.2%、
Al:0.0001~0.05%、
Ti:0.0001~0.030%及び
B :0.0001~0.0005%
を含有し、残部は鉄及び不可避的不純物の成分組成になり、板厚中心部の鋼組織が、有効結晶粒径で2~10μm、ベイナイト及びアシキュラーフェライトの面積率の合計で60~99%であるとともに、任意の2部位におけるベイナイト及びアシキュラーフェライトの面積率の合計を、それぞれ、A及びBとしたとき、A-Bの絶対値が0~30%であり、かつ、板厚が7~25mmであり、幅方向の引張強度TSが400~700MPaであることを特徴とするラインパイプ用ホットコイル。 - 前記ホットコイルが、さらに、質量%で、
Cu:0.01~0.5%、
Ni:0.01~1.0%、
Cr:0.01~1.0%、
Mo:0.01~1.0%、
V :0.001~0.10%、
W :0.0001~0.5%、
Zr:0.0001~0.050%
Ta:0.0001~0.050%
Mg:0.0001~0.010%、
Ca:0.0001~0.005%、
REM:0.0001~0.005%、
Y :0.0001~0.005%、
Hf:0.0001~0.005%及び
Re:0.0001~0.005%
のうち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に記載のラインパイプ用ホットコイル。 - 質量%で、
C :0.03~0.10%、
Si:0.01~0.50%、
Mn:0.5~2.5%、
P :0.001~0.03%、
S :0.0001~0.0030%、
Nb:0.0001~0.2%、
Al:0.0001~0.05%、
Ti:0.0001~0.030%及び
B :0.0001~0.0005%
を含有し、残部は鉄及び不可避的不純物の成分組成になる鋼片を、1000~1250℃に加熱した後、熱間圧延するに際し、再結晶温度域での圧下比を1.9~4.0、かつ、再結晶温度域での各圧延パス間で少なくとも1回、熱間圧延中の鋼板を100~500秒間滞留させて、得られた熱間圧延鋼板を、前段と後段に分けて冷却するにあたり、前段の冷却では、前記熱間圧延鋼板の表面温度が、前段の冷却開始温度から600℃となるまで、熱間圧延鋼板の板厚中心部で0.5~15℃/秒の冷却速度で冷却し、後段の冷却では、熱間圧延鋼板の板厚中心部で前段よりも速い冷却速度で冷却することを特徴とするラインパイプ用ホットコイルの製造方法。 - 前記鋼片が、さらに、質量%で、
Cu:0.01~0.5%、
Ni:0.01~1.0%、
Cr:0.01~1.0%、
Mo:0.01~1.0%、
V :0.001~0.10%、
W :0.0001~0.5%、
Zr:0.0001~0.050%
Ta:0.0001~0.050%
Mg:0.0001~0.010%、
Ca:0.0001~0.005%、
REM:0.0001~0.005%、
Y :0.0001~0.005%、
Hf:0.0001~0.005%及び
Re:0.0001~0.005%
のうち1種又は2種以上を含有することを特徴とする請求項3に記載のラインパイプ用ホットコイルの製造方法。 - 未再結晶温度域での圧下比を2.5~4.0で熱間圧延することを特徴とする請求項3又は4に記載のラインパイプ用ホットコイルの製造方法。
- 前記前段の冷却を、800~850℃の温度域から開始し、800~600℃の温度域を、板厚中心部で0.5~10℃/秒の冷却速度で冷却することを特徴とする請求項3又は4に記載のラインパイプ用ホットコイルの製造方法。
- 前記前段の冷却を、800~850℃の温度域から開始し、800~600℃の温度域を、板厚中心部で0.5~10℃/秒の冷却速度で冷却することを特徴とする請求項5に記載のラインパイプ用ホットコイルの製造方法。
- 前記後段の冷却後の鋼板を、450~600℃で巻き取ることを特徴とする請求項3又は4に記載のラインパイプ用ホットコイルの製造方法。
- 前記後段の冷却後の鋼板を、450~600℃で巻き取ることを特徴とする請求項5に記載のラインパイプ用ホットコイルの製造方法。
- 前記後段の冷却後の鋼板を、450~600℃で巻き取ることを特徴とする請求項6に記載のラインパイプ用ホットコイルの製造方法。
- 前記後段の冷却後の鋼板を、450~600℃で巻き取ることを特徴とする請求項7に記載のラインパイプ用ホットコイルの製造方法。
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| EP3026140A4 (en) * | 2013-07-25 | 2017-03-08 | Nippon Steel & Sumitomo Metal Corporation | Steel plate for line pipe, and line pipe |
| JP2015054983A (ja) * | 2013-09-11 | 2015-03-23 | Jfeスチール株式会社 | 高靭性高延性高強度熱延鋼板及びその製造方法 |
| JP2017504722A (ja) * | 2013-12-24 | 2017-02-09 | ポスコPosco | 溶接熱影響部の靱性に優れた超高強度溶接構造用鋼材及びその製造方法 |
| US11377719B2 (en) | 2016-06-22 | 2022-07-05 | Jfe Steel Corporation | Hot-rolled steel sheet for heavy-wall, high-strength line pipe, welded steel pipe for heavy-wall, high-strength line pipe, and method for producing the welded steel pipe |
| WO2017221690A1 (ja) | 2016-06-22 | 2017-12-28 | Jfeスチール株式会社 | 厚肉高強度ラインパイプ用熱延鋼板、ならびに、厚肉高強度ラインパイプ用溶接鋼管およびその製造方法 |
| KR20190007463A (ko) | 2016-06-22 | 2019-01-22 | 제이에프이 스틸 가부시키가이샤 | 후육 고강도 라인 파이프용 열연 강판, 그리고, 후육 고강도 라인 파이프용 용접 강관 및 그 제조 방법 |
| JP2018104757A (ja) * | 2016-12-26 | 2018-07-05 | 新日鐵住金株式会社 | ラインパイプ用鋼材及びその製造方法 |
| WO2019131100A1 (ja) * | 2017-12-25 | 2019-07-04 | Jfeスチール株式会社 | 熱延鋼板およびその製造方法 |
| JP2019112676A (ja) * | 2017-12-25 | 2019-07-11 | Jfeスチール株式会社 | 熱延鋼板およびその製造方法 |
| US11390931B2 (en) | 2017-12-25 | 2022-07-19 | Jfe Steel Corporation | Hot-rolled steel plate and method for manufacturing same |
| JP2022536627A (ja) * | 2019-06-24 | 2022-08-18 | ポスコ | 耐腐食性に優れた高強度構造用鋼材及びその製造方法 |
| JP7348963B2 (ja) | 2019-06-24 | 2023-09-21 | ポスコ カンパニー リミテッド | 耐腐食性に優れた高強度構造用鋼材及びその製造方法 |
| WO2024096073A1 (ja) * | 2022-11-02 | 2024-05-10 | 日本製鉄株式会社 | 熱延コイル |
| JP2024106089A (ja) * | 2023-01-26 | 2024-08-07 | Jfeスチール株式会社 | 鋼管杭継手用電縫鋼管、鋼管杭継手および鋼管杭 |
| JP7726224B2 (ja) | 2023-01-26 | 2025-08-20 | Jfeスチール株式会社 | 鋼管杭継手用電縫鋼管、鋼管杭継手および鋼管杭 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2749668B1 (en) | 2016-07-06 |
| CN103328673A (zh) | 2013-09-25 |
| TW201331386A (zh) | 2013-08-01 |
| EP2749668A4 (en) | 2015-07-01 |
| KR101436773B1 (ko) | 2014-09-01 |
| KR20130116928A (ko) | 2013-10-24 |
| US9062363B2 (en) | 2015-06-23 |
| US20140190597A1 (en) | 2014-07-10 |
| CN103328673B (zh) | 2014-10-22 |
| JP5339006B1 (ja) | 2013-11-13 |
| EP2749668A1 (en) | 2014-07-02 |
| RU2553172C1 (ru) | 2015-06-10 |
| MX2013009560A (es) | 2013-09-06 |
| TWI432585B (zh) | 2014-04-01 |
| JPWO2013047702A1 (ja) | 2015-03-26 |
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