tubular materials from oil fields and production methods

专利摘要:
tubular oil field materials and production methods thereof the present invention relates to a steel for tubular oil field materials which includes, as chemical composition, in mass%, c, si, mn, al, mo, P. s, o, ne balance containing fe and impurities, where the total width at half the maximum hw of a crystal plane corresponding to a crystal plane (211) of a phase and a carbon content expressed in% by mass in the chemical composition satisfying hw x c1 / 2 £ 0.38, the carbon content and molybdenum content expressed in% by mass in the chemical composition satisfy cx mo ³ 0.6, the number of carbides m2c having a hexagonal crystal structure and having a equivalent circle diameter of 1 nm or more is 5 pieces or more per square micron, and the yield limit is 758 mpa or more.
公开号:BR112014030346B1
申请号:R112014030346
申请日:2013-06-17
公开日:2020-05-05
发明作者:Sakamoto Akihiro；Kawano Kaori；Okamura Kazuo；Kondo Keiichi；Yamamoto Kenji；Nagahashi Koji；Seo Masanao；Omura Tomohiko；Arai Yuji
申请人:Nippon Steel & Sumitomo Metal Corp；Nippon Steel Corp；
IPC主号:

专利说明:

Descriptive Report of the Invention Patent for TUBULAR MATERIALS OF OIL FIELDS AND PRODUCTION METHODS OF THE SAME.
TECHNICAL FIELD [001] The present invention relates to steel for tubular materials from oil fields and a method of producing it. In particular, the present invention relates to a low-alloy steel for tubular oilfield materials that is used for tubular materials from oilfields such as a housing, pipe, and the like for an oil well and a gas well , and a method of producing it.
[002] Priority is claimed over Japanese Patent Application No. 2012-138650, filed on June 20, 2012, the content of which is incorporated herein by reference.
BACKGROUND [003] For tubular materials from oil fields, high reinforcement is required with the deepening of wells such as oil wells and gas wells (hereinafter collectively referred to simply as an oil well). Conventionally, tubular materials from oil fields of grade 80 ksi (the yield limit is 80 ksi, ie 551 to 654 MPa) or grade 95 ksi (the yield limit is 95 ksi, ie 654 to 758 MPa) were widely used. However, in recent years, 110 ksi grade tubular materials for oil fields (the yield limit is 110 ksi, that is, 758 to 862 MPa) are beginning to be used.
[004] In addition, most deep wells, which were developed in recent years, contain hydrogen sulfide having corrosivity. Therefore, it is necessary that tubular materials for oil fields have not only high strength, but also high resistance to fracture under stress in the presence of sulfide (hence
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2/70 onwards referred to as SSC resistance).
[005] Methods, in which steel is purified or a steel structure is refined, are known as an improvement plan for the SSC strength of conventional tubular materials for grade 95 to 110 ksi oil fields. For example, an unexamined Japanese Patent Application, First Publication No. S62-253720 suggests a method of improving SSC resistance by reducing impurity elements such as Mn, P and the like. An Unexamined Japanese Patent Application, First Publication No. S59-232220 suggests a method of improving SSC strength by performing a hardening treatment twice to refine the crystal grain.
[006] In response to the demand for the high reinforcement of tubular materials for oil fields, in recent years, a steel for tubular materials for oil fields of grade 125 ksi has been suggested (the yield limit is 862 to 965 MPa). However, stress fracture in the presence of sulfide (SSC) tends to occur with an increase in strength. Therefore, in relation to steel for tubular materials for oil fields of grade 125 ksi or greater, another improvement in SSC resistance is required compared to conventional steel for tubular materials for oil fields of grade 95 ksi or grade 110 ksi.
[007] An Unexamined Japanese Patent Application, First Publication No. H6-322478, An Unexamined Japanese Patent Application, First Publication No. H8-311551, An Unexamined Japanese Patent Application, First Publication No. H11-335731 , an unexamined Japanese Patent Application, First Publication No. 2000-178682, an unexamined Japanese Patent Application, First Publication No. 2000-256783, 297344, an unexamined Japanese Patent Application, First Publication No. 2000-119798 , an Unexamined Japanese Patent Application, First Publication No.
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3/70
2005-350754, an Unexamined Japanese Patent Application, First Publication No. 2006-265657, Unexamined Japanese Patent Application, First Publication No. 2000-313919, and a PCT International Publication No. 2007/007678 suggest improvement plans for SSC resistance of high strength steel for tubular oilfield materials.
[008] An Unexamined Japanese Patent Application, First Publication No. H6-322478 suggests a method of improving the SSC resistance of 125 ksi grade steel materials by refining the steel structure through an induction heating treatment . An unexamined Japanese Patent Application, First Publication No. H8-311551 suggests a method of improving the SSC strength of steel tubes from grade 110 ksi to grade 140 ksi in a case of increased hardening capacity by using a method of direct quenching and increasing tempering temperature. An unexamined Japanese Patent Application, First Publication No. H11335731 suggests a method of improving the SSC strength of 110 ksi grade low alloy steel to 140 ksi through an optimal fit of a bonding component. An Unexamined Japanese Patent Application, First Publication No. 2000-178682, an Unexamined Japanese Patent Application, First Publication No. 2000-256783, and an Unexamined Japanese Patent Application, First Publication No. 2000-297344 suggest a method of improving the SSC resistance of low alloy steel for tubular materials from oil fields from 110 ksi to 140 ksi by controlling the carbide morphology. An unexamined Japanese Patent Application, First Publication No. 2000-119798 suggests a method of delaying the SSC occurrence time of 110 ksi grade steel materials by allowing fine V carbides to precipitate sufficiently. Japanese Patent Application Not Examined, First Publication No. 2005
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4/70
350754 suggests a method of improving the SSC strength of tubular materials for oil fields of 125 ksi or greater by controlling the displacement density and hydrogen diffusion coefficient to desired values. An unexamined Japanese Patent Application, First Publication No. 2006-265657 suggests a method of improving the SSC strength of steel for field and oil tubular materials of 125 ksi or greater by allowing a large amount of C to be contained, interrupting water cooling to 400 to 600 ° C during water cooling, and perform heat treatment and isothermal transformation (ausrevention treatment) at 400 to 600 ° C to form a single phase bainite structure. An unexamined Japanese Patent Application, First Publication No. 2000-323919 and an International PCT Publication No. 2007/007678 describe a method of improving the SSC strength of steel tubes by increasing the Mo content compared to conventional tubular materials. oil fields.
RELATED TECHNICAL DOCUMENTS
PATENT DOCUMENTS [009] Patent Document 1 - Unexamined Japanese Patent Application, First Publication No. S62-253720 [0010] Patent Document 2 - Unexamined Japanese Patent Application, First Publication No. S59-232220 [0011] Patent 3 - Unexamined Japanese Patent Application, First Publication No. H6-322478 [0012] Patent Document 4 - Unexamined Japanese Patent Application, First Publication No. H8-311551 [0013] Patent Document 5 - Japanese Patent Application No examined, First Publication ° H11-335731 [0014] Patent Document 6 - Japanese Patent Application not examined, First Publication ° 2000-178682
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5/70 [0015] Patent Document 7 - Unpublished Japanese Patent Application, First Publication ⁰ 2000-256783 [0016] Patent Document 8 - Unexamined Japanese Patent Application, First Publication ⁰ 2000-297344 [0017] Patent 9 - Unexamined Japanese Patent Application, First Publication ⁰ 2000-119798 [0018] Patent Document 10 - Unexamined Japanese Patent Application, First Publication ⁰ 2005-350754 [0019] Patent Document 11 - Japanese Patent Application No examined, First Publication ⁰ 2006-265657 [0020] Patent Document 12 - Japanese Patent Application Unexamined, First Publication ⁰ 2000-313919 [0021] Patent Document 13 - PCT International Publication No. 2007/007678
DESCRIPTION OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION [0022] As described above, in recent years, another improvement in the SSC strength of steel was required for 110 ksi grade oilfield tubular materials (yield limit is 758 MPa or more) or 125 ksi or greater (the yield limit is 862 MPa or more). This is because oil wells and gas wells currently in use contain a lot of hydrogen sulfide. For example, an Unexamined Japanese Order, First Publication No. 2005-350754 and an Unexamined Japanese Order, First Publication 2006-265657 describe a steel for tubular oilfield materials that has a flow limit of 125 degrees ksi and that is excellent in SSC resistance. However, all test baths used to assess SSC resistance are test baths in which 0.1 atm hydrogen sulfide is saturated. Therefore, in high-strength steel for tubular materials
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6/70 of oil fields, excellent SSC resistance is required even in a test bath in which the ultra high pressure hydrogen sulfide is saturated.
[0023] In addition, tubular materials from conventional oil fields having a flow limit of 110 ksi or greater are not suitable for use in pipelines. Tubular oil hood materials having a grade flow limit of 95 ksi or less are used in pipe and pipe housings. However, in tubular materials from oil fields having a flow limit of 110 ksi or greater, the SSC resistance in a case where the notch is applied (value of the stress intensity factor Kissc in a hydrogen sulfide environment) is decreased. Therefore, in a case where conventional tubular materials from oil fields of 110 ksi or greater are used as piping that is directly exposed to a production fluid, SSC can occur from a latent defect or corrosion latent microfissure as a starting point. Consequently, in relation to steel for tubular oilfield material having resistance of 110 ksi or greater, it is preferable that the Kissc value is high to be applied to the pipes.
[0024] The present invention should provide a low alloy steel for tubular oil field materials excellent in SSC resistance. Specifically, the present invention should provide low-alloy steel for oilfield tubular materials, which has a yield limit (0.2% proof stress) of 110 ksi or greater (758 MPa or more) or grade of 125 ksi or greater (862 MPa or more), and which is excellent in SSC resistance containing the SSC resistance in the high pressure hydrogen sulfide environment, the SSC resistance in the case where the notch is applied, and the like. SOLUTION TO THE PROBLEM
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7/70 [0025] One aspect of the present invention employs the following:
(1) A low alloy steel for tubular oilfield materials according to one aspect of the present invention includes, as a chemical composition, in% by mass, C: more than 0.35% to 1.00%, Si: 0, 05% to 0.5%, Mn: 0.05% to 1.0%, Al: 0.005% to 0.10%, Mo: more than 1.0 to 10%, P: 0.025% or less, S: 0.010% or less, O: 0.01% or less, N: 0.03% or less, Cr: 0% to 2.0%, V: 0% to 030%, Nb: 0% to 0.1% , Ti: 0% to 0.1%, Zr: 0% to 0.1, Ca: 0% to 0.01%, B: 0% to 0.003%, and the balance consisting of Fe and impurities, where, when the total width in half of a maximum of the crystal plane corresponding to the crystal plane (211) of a phase, which is obtained by X-ray diffraction, is an HW in ° units, the total width in half of a maximum HW and p carbon content expressed in% by mass in the chemical composition satisfy Expression 1 below, the carbon content and molybdenum content expressed in% by mass in the chemical composition satisfy Expression 2 below, the number of M2C carbides having a d structure and hexagonal crystal and having an equivalent circle diameter of 1 nm or more is 5 particles or more per square micron, and the yield limit is 758 Mpa or more.
HW x C ^1/2 <0.38 (Expression 1) C x Mo> 0.6 (Expression 2) [0026] Low alloy steel for oilfield tubular materials according to the aspect of the invention has excellent SSC resistance.
(2) In low alloy steel for tubular materials from oil fields as per item (1), steel may include, as a chemical composition, in mass%, Cr: 0.1 to 2.0%.
(3) In low alloy steel for oilfield tubular materials as per item (1) or (2), Steel may include, as
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8/70 chemical composition, in% by mass, V: 0.05% to 0.30%.
(4) In low alloy steel for tubular materials from oil fields according to item (1) to (3), steel may include, as a chemical composition, in mass%, at least one element between Nb: 0.002% a 0.1%, Ti: 0.002% to 0.1%, and Zr: 0.002% to 0.1%.
[0027] In low-alloy steel for tubular materials from oil fields as per item (1) to (4), Steel may include, as a chemical composition, in mass%, Ca: 0.0003% to 0.01 %.
[0028] In low alloy steel for tubular materials from oil fields as per item (1) to (5), Steel may include, as chemical composition, in mass%, B: 0.0003% to 0.003%.
[0029] A method for producing low-alloy steel for tubular oilfield materials according to one aspect of the invention includes: a hot rolling process of hot working a steel part, which includes as a chemical composition, in% by mass, C: more than 0.35% to 1.00%, Si: 0.05% to 0.5%, Mn: 0.05% to 1.0%, Al: 0.005% to 0.10% , Mo: more than 1.0% to 10%, P: 0.025% or less, S: 0.010% or less, O: -0.1% or less, N: 0.03% or less, Cr: 0% 2.0%, V: 0% to 0.30%, Nb: 0% to 0.1%, Ti: 0% to 0.1%, Zr: 0% to 0.1%, Ca: 0% at 0.01%, B: 0% to 0.003%, and the balance consisting of Fe and impurities and in which a carbon content and a molybdenum content expressed in mass% in the chemical composition satisfy Expression 2 below, for get a steel material; a quenching process of rapidly cooling the steel material after the hot working process; and a tempering process of tempering the steel material after the tempering process over a tempering range of 680 ° C to an Aci point.
C x Mo> 0.6 (Expression 2) (8) In the production method of low alloy steel for tubular materials from oil fields as per item (7), in the process
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9/70 s of quenching, the steel material after the hot working process can be cooled quickly by continuous cooling under a condition in which the time taken from the temperature of beginning of quenching to the temperature of beginning of transformation into martensite it's 100 seconds to 600 seconds.
[0030] In the production method of low alloy steel for tubular materials from oil fields according to item (7), in the tempering process, as the first cooling treatment, the steel material after the hot working process can be cooled under a condition where the cooling rate from the tempering start temperature to the temperature range greater than one Ms point at 300 ° C is 0.7 ° C / s or more, as an isothermal treatment, the material steel after the first cooling treatment can be maintained under a condition in the temperature range of greater than Ms point up to 300 ° C, and as a second cooling treatment, the steel material after the isothermal treatment can be cooled.
(10) In the production method of low alloy steel for tubular materials from oil fields according to any of the items (7) to (9), in the cooling process, when a Rockwell hardness in scale C in a central portion of the thickness of the steel material after the tempering process and before the tempering process is an HRC, the steel material can be cooled quickly under a condition where Rockwell HRC hardness meets Expression 3 below.
HRC> 50 x C + 26 (Expression 3) (11) The production method of low-alloy steel for tubular oilfield products in accordance with any of items (7) to (10) may also include a process for standardizing the steel material after the hot working process and before the tempering process.
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10/70 [0031] The production method of low alloy steel for tubular materials from oil fields according to any of the items (7) to (11), the steel part can include as chemical composition, in mass%, Cr: 0.1% to 2.0%.
(13) In the production method of low alloy steel for tubular materials from oil fields according to any of the items (7) to (12), the steel part may include, as chemical composition, in mass%, V: 0.05% to 0.30%;
(14) In the production method of low alloy steel for tubular materials from oil fields according to any of the items (7) to (13), the steel part may include, as chemical composition, in mass%, at least an element between Nb: 0.002% to 0.1%, Ti: 0.002% to 0.1%, and Zr: 0.002% to 0.1%.
(15) In the production method of low alloy steel for tubular materials from oil fields according to any of items (7) to (14), the steel part may include, as chemical composition, in mass%, Ca: 0.0003% to 0.01%.
(16) In the production method of low alloy steel for tubular materials from oil fields according to any of items (7) to (15), the steel part may include, as chemical composition, in mass%, B: 0.0003% to 0.003%.
ADVANTAGE EFFECTS OF THE INVENTION [0032] Low alloy steel for oilfield tubular materials according to the aspect of the invention has excellent SSC resistance.
[0033] Low alloy steel for oilfield tubular materials produced by the aspect of the invention has excellent SSC resistance.
[0034] Specifically, it is possible to supply low-alloy steel for tubular materials from oil fields, which has an imitate
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11/70 flow (0.2% test stress) of 110 ksi or greater (758 MPa or more) or 125 ksi or greater (862 MPa or more), and which is excellent in SSC resistance containing SSC resistance in the high pressure hydrogen sulfide environment, SSC resistance in the case where the notch is applied, and the like.
BRIEF DESCRIPTION OF THE DRAWINGS [0035] FIG. 1A is a microphotograph of an electronically transmitted microscope of hexagonal M2C carbides that are contained in a low-alloy steel for tubular materials from oil fields according to one embodiment of the present invention.
[0036] FIG. 1B is an electronic diffraction pattern and a view illustrating the result of the identification of the hexagonal M2C carbides that are contained in low alloy steel for tubular materials from oil fields according to the modality.
[0037] FIG. 2 is an X-ray diffraction pattern of carbides that are residues from the electrolytic extraction of low-alloy steel for tubular materials from oil fields according to the modality.
[0038] FIG. 3 is a view explaining a tempering process in a production method of a low alloy steel for tubular materials from oil fields according to a modality of the present invention and a view illustrating the tempering process including a continuous cooling treatment and a process hardening including an isothermal treatment.
[0039] FIG. 4 is a view illustrating the relationship between the thickness t (mm) of a steel tube and the CR8-5 cooling rate (° C / s) to suppress temper fractures during tempering in the continuous cooling treatment.
DESCRIPTION OF MODALITIES [0040] Hereinafter, a preferred embodiment of the invention in relation to the drawings will be described in detail. In the drawings, the
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12/70 same reference sign will be given to the same parts or corresponding parts in the drawings, and their description will be omitted here. The% relative to an element in the chemical composition represents% by mass.
[0041] The present inventors have examined and investigated the SSC resistance of low-alloy steel for tubular materials from oil fields, and obtained the following findings:
(A) When hexagonal M2C carbides are formed in low alloy steel for oilfield tubular materials, SSC resistance increases. Here, hexagonal M2C carbides represent M2C carbides having a hexagonal crystal structure. M of M2C represents Mo, or Mo and V.
[0042] Mo and C promote the formation of hexagonal M2C carbides which are fine carbides. FIG. 1A shows a microphotograph of an electronic transmission microscope (TEM) of low-alloy steel for tubular materials from oil fields according to the modality of the invention. Hexagonal M2C carbides are thin plate-shaped carbides, and their grain size is approximately 1 nm to 50 nm in an equivalent circle diameter. Hexagonal M2C carbides are different from M2C carbides that have a cubic crystal structure. Hexagonal M2C carbides are plate-shaped, and thus tend to trap diffuse hydrogen. It appears that the hexagonal M2C carbides strongly trap hydrogen and the trapped hydrogen becomes inactive, so the occurrence of SSC is suppressed. In addition, hexagonal M2C carbides are thin, and thus hardly act as a starting point for SSC. Consequently, hexagonal M2C carbides contribute to an improvement in SSC strength. Hexagonal M2C carbides can be identified by observation under an electron microscope and electron beam diffraction as described below. In
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13/70 addition, in relation to the presence of hexagonal M2C carbides, the presence itself can be confirmed by X-ray diffraction of an electrolytically extracted residue as described below.
[0043] When five pieces or more of hexagonal M2C carbides having a grain size (equivalent circle diameter) of 1 nm or more are present in a square micron (pm ² ), the SSC resistance of low alloy steel for tubular materials of oil fields increases. In addition, there is a possibility that hexagonal M2C carbides having a grain size of less than 1 nm may be present. However, the identification of hexagonal M2C carbides of less than 1 nm by the electron microscope and by electron beam diffraction is technically difficult. Therefore, in the invention, the number of hexagonal M2C carbides having a grain size of i nm or more per unit area is provided.
(B) Mo content must be greater than 1% and 10% or less. In this case, not only is the formation of the hexagonal M2C carbides described above, but also the penetration of hydrogen into the steel under a hydrogen sulfide environment is suppressed. Specifically, Fe sulfide, which is a corrosion product, is formed on a steel surface under the hydrogen sulfide environment. Mo focuses on Fe sulfide, and increases the protective performance of Fe sulfide on the steel surface. Consequently, the penetration of hydrogen into the steel under hydrogen sulfide environment is suppressed, and thus the SSC resistance increases.
(C) In low-alloy steel for oilfield tubular materials, various carbides in addition to hexagonal M2C carbides are also formed during tempering and tempering. Among the carbides, M3C carbides and M23C6 carbides that are formed mainly at the grain edges or at the truss interfaces of the martensite structure are defined as carbides of
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14/70 grain contour in the invention. Here M of M3C carbides and M23C6 carbides represent Fe, Cr or Mo.
[0044] Grain boundary carbides are much larger than hexagonal M2C carbides and are several hundred nm in size. Since the grain boundary carbides are large, when the shape of the grain boundary carbides is flat, the stress fracture in the presence of sulfide (SSC) tends to occur in the grain boundary carbides as a starting point. On the other hand, when the shape of grain boundary carbides must be spherical, SSC is difficult to occur in grain boundary carbides, and thus SSC resistance is improved. Consequently, in order to improve the SSC resistance, it is preferable to coalesce the grain boundary carbides.
[0045] Grain boundary carbides can be coalesced to some extent by an increase in tempering temperature. However, the coalescence of grain bound carbides by increasing the tempering temperature has a limit. It is also preferable to coalesce the grain boundary carbides by a different method than the method of increasing the tempering temperature.
[0046] When the C content is increased, specifically when the C content is increased to be greater than 0.35%, the grain boundary carbides in the steel can also be coalesced. Consequently, the SSC resistance also increases. It is assumed that the reason why grain boundary carbides are coalesced when the C content is increased is as follows. When the C content increases, the total grain bound carbides increase. Consequently, the concentration of Cr and Mo in each grain boundary carbide decreases, so that the grain boundary carbides are coalesced.
(D) When the displacement density in steel is high, the SSC resistance decreases. This is because the displacement acts as a
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15/70 hydrogen prison site. It appears that the displacement weakly traps the hydrogen by the Cottrel effect and the trapped hydrogen is able to diffuse again, so that the fragility of the hydrogen occurs by diffusion to a tip of the sulfide stress fracture (SSC). In other words, when the hexagonal M2C carbides are contained and the travel density is low, the hydrogen in the steel is preferably and strongly trapped in the hexagonal M2C carbides. As a result, SSC resistance is improved. Consequently, it is preferable that the displacement density is low.
[0047] The total width in the middle of a maximum of the crystal plane in X-ray diffraction is affected by the density of displacements. Specifically, the total width in half a maximum is increased with an increase in the travel density. Consequently, in the invention, the total width in half of a maximum HW (*) of a diffraction peak of the crystal plane (211), which is obtained by X-ray diffraction, is considered as a parameter that indicates the tension in the truss. . The tension in the truss increases with increasing displacement density. In a case in which the C content is greater than 0.35% and the amount of Mo is greater than 1%, when the width of the medium in half of the maximum HW satisfies the expression 1, the displacement density in the steel is sufficiently low, and excellent SSC resistance can be obtained.
HW x C ^1/2 <0.38 (Expression 1) [0048] Here, the carbon content (% by mass) is replaced by C in Expression 1.
[0049] Low-alloy steel for tubular materials from oil fields according to the modality includes mainly, such as metallographic structure, tempered martensite and tempered bainite. However, since martensite, bainite and ferrite correspond to the crystal structure of the BCC (body-centered cubic) or a structure that incorporates it
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16/70 clua, it is difficult to distinguish martensite, bainite and ferrite by the X-ray diffraction method. In the invention, martensite, bainite and ferrite are considered to be a phase. Consequently, the total width at half the maximum HW of the diffraction peak of the crystal plane (211) represents the total width at half the maximum of a crystal plane corresponding to the crystal plane (211) of phase a.
[0050] As described above. In a range of chemical composition that is specified in the modality, when five pieces or more of hexagonal M2C carbides having a grain size of 1nm the most fall into a square micron (pm ² ) and the total width in half of the maximum HW satisfies the Expression 1, an excellent SSC resistance can be obtained.
[0051] The present inventors carried out the invention based on the findings described above. Hereafter, low alloy steel for tubular materials from oil fields will be described according to the modality.
CHEMICAL COMPOSITION [0052] Low alloy steel for tubular materials from oil fields according to the modality has the following chemical composition. % in the contents of the respective elements as described below expressed in mass%. In addition, the limiting range of the respective elements as described below includes its lower limit and its upper limit. However, the limiting range in which the lower limit is shown with more than does not include the lower limit, and the limiting range in which the upper limit is shown as less than [0053] does not include the upper limit.
[0054] Low alloy steel for tubular materials from oil fields according to the modality includes, as basic elements, C, Si, Mn, Al and Mo.
C: more than 035% to 1.00%
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17/70 [0055] In low alloy steel for tubular materials from oil fields according to the modality, the amount of carbon (C) is greater than that of conventional low alloy steel for tubular materials from oil fields. When a large amount of C is contained, coalescence of the grain boundary carbides is promoted, and thus the SSC strength of the steel is improved. On the other hand, when C is excessively contained, the effect is saturated. Consequently, the amount of C must be greater than 0.35% and 1.00% or less. The lower limit of the amount of C is preferably 0.45%, more preferably 0.51%, and even more preferably 0.56%. The upper limit of the amount of C is less than 1.00%, more preferably 0.80%, and even more preferably 0.70%.
Si: 0.05% to 0.5% [0056] Silicon (Si) deoxides steel. On the other hand, when Si is excessively contained, the effect is saturated. Consequently, the amount of Si must be 0.05% to 0.5%. The lower limit of the amount of Si is preferably greater than 0.05%, more preferably 0.1% and even more preferably 0.13%., The upper limit of the amount of Si is preferably less than 0.5%, more preferably 0.40%, and even more preferably 0.30%.
Mn: 0.05% to 10% [0057] Manganese (Mn) increases the hardening capacity of steel. On the other hand, when Mn is excessively contained, manganese secretes at the grain edges along with impurity elements such as phosphorus (P), sulfur (S), and the like. As a result, the SSC resistance of the steel decreases. Consequently, the amount of Mn should be 0.05% to 1.0%. The lower limit of the amount of Mn is preferably greater than 0.05%, more preferably 0.10%, and even more preferably 0.35%. The upper limit of the amount of Mn is preferably less than 1.0%, more preferably 0.70%,
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18/70 more preferably 0.65%, and even more preferably 0.50%.
Al: 0.005% to 0.10% [0058] Aluminum (Al) deoxides steel. On the other hand, when Al is excessively contained, the effect is saturated, and the inclusions increase. Consequently, the amount of Al should be 0.005% to 0.10%. The lower limit of the amount of Al is preferably greater than 0.005%, more preferably 0.010%, and even more preferably 0.020%. The upper limit of the amount of Al is preferably less than 0.10%, more preferably 0.06%, and even more preferably 0.05%. In the embodiment, the amount of Al represents acid-soluble Al, that is, the amount of Al.sol.
Mo: more than 1.0% to 10% [0059] Molybdenum increases the hardening capacity, and increases the fraction of martensite in a structure. Consequently, Mo increases the strength of the steel. In addition, the concentration of Mo in the Fe sulfide (corrosion product) that is formed on the steel surface under the hydrogen sulfide environment, and increases the protective performance of the Fe sulfide on the steel surface. Consequently, the penetration of hydrogen into the steel is suppressed, and thus the SSC resistance of the steel increases. In addition, Mo forms the hexagonal Mo2C carbides which are fine carbides. Hexagonal Mo2C carbides fix (trap) diffuse hydrogen so that the occurrence of SSC due to hydrogen is suppressed. On the other hand, when Mo is excessively contained, the effect is saturated. Consequently, the amount of Mo must be greater than 1.0% and 10% or less. The lower limit of the amount of Mo is preferably 1.20%, hands preferably 1.30%, and even more preferably 1.55%. The upper limit of the amount of Mo is preferably less than 10%, is preferably 4.0%, and even more preferably 3.0% [0060] Low alloy steel for tubular field materials
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19/70 oil according to the modality includes impurities. Here, impurities represent elements that are contaminated during the industrial production of steel from ores and scrap that are used as raw material for steel, or the environment of a production process. Among the impurities, it is preferable that P S, O and N are limited to the following values to sufficiently obtain the effects mentioned above. In addition, since it is preferable that the amount of the respective impurities is low, the lower limit need not be limited, and the lower limit of the respective impurities can be 0%.
P: 0.025% or less [0061] Phosphorus (P) is an impurity. P secretes at the grain edges and decreases the SSC resistance of the steel. Therefore, it is preferable that the amount of P is small. Consequently, the amount of P is preferably less than 0.025%, more preferably 0.020% or less, and even more preferably 0.015% or less.
S: 0.010% or less [0062] Sulfur (S) is an impurity in common with P. S secretes at the grain edges, and decreases the SSC resistance of the steel. Therefore, it is preferable that the amount of S is small. Consequently, the amount of S must be 0.10% or less. The amount of S is preferably less than 0.010%, more preferably 0.005% or less, and even more preferably 0.003% or less.
O: 0.010% or less [0063] Oxygen (O) is an impurity. When O is excessively contained, crude oxides are formed, and thus the toughness and SSC strength of the steel decrease. Therefore, it is preferable that the amount of O is small. Consequently, the amount of O should be 0.01% or less, and more preferably 0.005% or less.
N: 0.03% or less [0064] Nitrogen is an impurity. When N is excessive Petition 870190106912, of 10/22/2019, p. 23/86
20/70 contained, crude nitrides are formed. Crude nitrides act as a starting point for localized corrosion, so that SSC resistance can decrease. Consequently, the amount of N must be 0.03% or less. The upper limit of the amount of N is preferably less than 0.03%, more preferably 0.025%, and even more preferably 0.02%. On the other hand, a small amount of nitrogen (N) binds to Nb, Ti and Zr to form nitrides or carbonitrides, which results in the refining of the steel structure by a fixing effect. Thus, the small amount of N can be consciously included in the steel. The lower limit of N to obtain the effect is preferably 0.003%, and more preferably 0.004%.
[0065] In addition, N is an impurity for steel production. In a case where the effects of the nitrides or carbonitrides described above are not positively required, N can be less than 0.003% as an impurity.
[0066] The chemical composition of low alloy steel for oilfield tubular materials according to the modality includes the basic elements mentioned above and additional elements as described below, and the balance consists of Fe and the impurities mentioned above. As described above, the impurities mentioned represent the elements that are contaminated by ores and scrap that are used as raw material for steel, or the environment of the production process.
OPTIONAL ELEMENTS [0067] The chemical composition of low alloy steel for tubular materials from oil fields according to the modality can also include at least one optional element between Cr, V, Nb, Ti, Zr, Ca and B in replacement of a part de Fe. Optional elements can be included if necessary. Thus, the lower limit of the respective optional elements need not be limited, and the lower limit
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21/70 can be 0%. In addition, even if the optional elements can be included as impurities, the effects mentioned above are not affected.
[0068] Low-alloy steels for oilfield tubular materials may also include Cr to replace part of the Fe.
Cr: 0% to 2% [0069] Chromium (Cr) is an optional element. Cr increases the hardening capacity of steel. Even when a small amount of Cr is contained, the effect can still be achieved. On the other hand, when Cr is excessively contained, the effect is saturated. Consequently, as needed, the amount of Cr should be 0% to 2%. The lower limit of the amount of Cr is preferably 0.5%. The upper limit of the amount of Cr is preferably less than 2%, more preferably 1.5%, more preferably 1.0%, more preferably less than 0.8%, and even more preferably 0.7%.
[0070] Low-alloy steel for oil well tubular materials may also include V to replace a part of Fe.
V: 0% to 0.30% [0071] Vanadium (V) forms the hexagonal M2C carbides, which are fine carbides, in combination with Mo, and thus the SSC resistance increases. Here, M of the hexagonal M2C carbides represents Mo and V. In addition, V forms MC carbides having a cubic crystal structure (M represents Mo and V), and thus increases the tempering temperature of the steel to obtain a high yield limit. MC cubic carbides are thin in contrast to grain bound carbides, and thus hardly act as a starting point for SSC. Even when a small amount of V is contained, the effect described above can be achieved. On the other hand, if V is excessively contained, the amount of solute-solid V in the quench is saturated
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22/70, and thus the effect of increasing the tempering temperature is also saturated. Consequently, as needed, the amount of V should be 0% to 0.30%. The lower limit of V is preferably 0.05%, more preferably 0.07%, and even more preferably 0.1%. The upper limit of the amount of V is preferably less than 0.30%, more preferably 0.25%, and even more preferably 0.20%.
[0072] Low alloy steel for tubular oilfield materials may also include at least one element selected from a group consisting of Nb, Ti and Zr to replace a part of Fe.
Nb: 0% to 0.1
Ti: 0% to 0.1%
Zr: 0% to 0.1% [0073] Niobium (Nb), titanium (Ti) and zirconium (Zr) are optional elements. The elements bond with C or N to form carbides, nitrides or carbonitrides. The precipitates (carbides, nitrides and carbonitrides) refine the structure of the steel by the fixation effect. Even when at least one element selected from the group consisting of Nb, Ti and Zr is contained in a small amount, the effect described above can be obtained. On the other hand, when Nb, Ti and Zr are excessively contained, the effect is saturated. Consequently, as needed, the amount of Nb must be 0% to 0.1%, the amount of Ti must be 0% to 0.1%, and the amount of Zr must be 0% to 0.1%. When the amount of Nb is 0.002% or more, the amount of Ti is 0.002% or more, or the amount of Zr is 0.002% or more, the effect described above can be significantly achieved. The lower limits of the amount of Nb, the amount of Ti, and the amount of Zr are more preferably 0.005%. The upper limits of the amount of Nb, the amount of Tim and the amount of Zr are preferably
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23/70
0.05%.
[0074] Low alloy steel for tubular materials from oil fields may also include Ca in replacement of a part of Fe. Ca: 0% to 0.01% [0075] Calcium (Ca) is an optional element. Ca binds to S in steel to form sulfides, and improves the shape of inclusions, with which SSC resistance increases. Even when a small amount of Ca is contained, the effect described above can be achieved. On the other hand, when Ca is excessively contained, the effect is saturated. Consequently, as needed, the amount of Ca should be 0% to 0.01%. The lower limit of the amount of Ca is preferably 0.0003%, and more preferably 0.0005%. The upper limit on the amount of Ca is preferably 0.0030%, and more preferably 0.002%.
[0076] Low-alloy steel for oilfield tubular materials may also include B in place of a part of Fe.
B: 0% to 0.003% [0077] Boron (B) is an optional element. B increases the hardening capacity of the steel. Even when a small amount of B is contained, the effect described above can be achieved. On the other hand, when B is excessively contained, the effect is saturated. Consequently, as needed, the amount of B should be 0% to 0.003%. The lower limit of the amount of B is preferably 0.0003%, and more preferably 0.0005%. The upper limit of the amount of B is preferably 0.0015%, and more preferably 0.0012%.
[0078] The metallographic structure of low alloy steel for tubular materials from oil fields according to the modality includes mainly tempered martensite and tempered bainite, and in addition, includes precipitates such as M2C carbides having structure
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24/70 hexagonal crystal.
(HEXAGONAL M2C CARBONES) [0079] Low alloy steel for oilfield tubular materials contains five pieces or more of the hexagonal M2C carbides per square micron (ie 5 particles / pm ² or more). Here, M2C carbides are carbides having a hexagonal crystal structure, and are different from M2C carbides having a cubic crystal structure. M of the hexagonal M2C carbides is Mo, or o and V.
[0080] The number of hexagonal M2C carbides is measured by the following method. Samples for TEM (electronically transmitted microscope) are collected from an arbitrary portion of low-alloy steel for tubular materials from oil fields, for example, from a portion including a central portion of the steel plate thickness of the steel tube. As a method for collecting the sample, methods such as the thin film method and an extraction replica method are used. 10 visual fields in the collected sample are observed by TEM to obtain TEM microphotographs of the respective visual fields. An area of each of the visual fields must be 1 pm ² . An electron beam diffraction pattern of the carbides in each visual field is confirmed to identify a type of carbide. FIG. 1B shows a pattern typical of the diffraction pattern of the hexagonal M2C carbides by observing the electron microscope. In addition, hexagonal M2C carbides can also be clearly distinguished from other carbides including cubic M2C carbides by X-ray diffraction. Consequently, confirmation of whether hexagonal M2C carbides precipitate or not may also be possible by performing ray diffraction. X of the extracted residue after electrolytically extracting the carbides in a steel material. FIG. 2 shows a diffraction pattern of X-ray diffraction. In FIG. 2, the horizontal axis represents 2Θ (°) of X-rays (considering that Θ is an angle
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25/70 incidence) and the vertical axis represents the diffraction intensity. MO2C and MC in FIG. 2 represent the type of carbides. Mo2C represents the hexagonal M2C carbides. MC represents MC cubic carbides (M represents Mo and V) or M2C cubic carbides. In FIG. 2, (021), (112) and the like represent crystal planes (miller indices). As shown in FIG. 2, the hexagonal M2C carbides can be clearly distinguished from other carbides including MC cubic carbides or cubic M2C carbides by X-ray diffraction.
[0081] The number of hexagonal M2C carbides that are identified in each visual field of observation with an electron microscope and have a grain size of 1 nm or more, is counted to calculate the average number per 1 pm ² . The calculated average number is defined as the number of hexagonal M2C carbides per 1 pm ² (parts / pm ² ). When the number of hexagonal M2C carbides is 5 particles / pm ² or more, excellent SSC resistance can be obtained.
[0082] The grain size of the hexagonal M2C carbides is approximately 1 nm to 50 nm. Here, the grain size of the hexagonal M2C carbides is measured by the following method. An area of each of the hexagonal M2C carbides is obtained by image analysis. The equivalent circle diameter of the area obtained is defined as the grain size of the hexagonal M2C carbides. As described above, in the embodiment, the number of hexagonal M2C carbides having a grain size of 1 nm or more is counted.
[0083] The upper limits on the number and grain size of the hexagonal M2C carbides are not particularly limited. However, hexagonal M2C carbides having a grain size of more than 50 nm are hardly observed, the upper limit of the grain size of hexagonal M2C carbides can be 50 nm.
[0084] Furthermore, as described above, in low alloy steel for
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26/70 tubular materials from oil fields depending on the modality, it is preferable that the shape of the grain boundary carbides is spherical. Specifically, between carbides, the average aspect ratio of grain boundary carbides such as M3C carbides and M23C6 carbides that are formed mainly at the grain edges of the lattice interfaces of the martensite structure is preferably 3 or less, and more preferably 2 or any less. Here, a value that divides the major axis by the minor axis of the grain boundary carbides in an observed section is defined as an aspect ratio. The aspect ratio is measured by the following method. Samples are taken from an arbitrary portion of low-alloy steel for tubular materials from oil fields, for example, from a portion including a central portion of the thickness of the steel plate or steel tube. 10 visual fields in the collected sample are observed by optical microscope, scanning electron microscope or electron transmission microscope. The aspect ratio of grain boundary carbides is measured in each visual field, and averaged.
[0085] In addition, as described above, in low alloy steel for oilfield tubular materials according to the modality, it is preferable that the displacement density is low although the hexagonal M2C carbides are contained.
TOTAL WIDTH IN HALF OF THE MAXIMUM HW [0086] In low alloy steel for tubular materials from oil fields according to the modality, the total width in half of the maximum (HW) (°) of the diffraction peak of the crystal plane corresponding to the plane crystal (211) of phase a, which is obtained by the X-ray diffraction method, satisfies Expression 1.
HX x C ^1/2 <0.38 (Expression 1) [0087] Here, the C content (% by mass) is replaced by the symbol for element C.
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27/70 [0088] The total width at half the maximum HW is measured by the X-ray diffraction method as follows. Specifically, samples are collected from arbitrary parts of low-alloy steel for tubular materials from oil fields, for example, from a part that includes the central portion of the thickness of the steel plate or steel tube. The surface of the collected sample is chemically polished. X-ray diffraction is performed on the chemically polished surface using Coka-ray (Ka1) as an incident X-ray. The total width at half the maximum of the crystal plane corresponding to the crystal plane (211) of the α phase is measured in units of °.
[0089] Specifically, Ka1 and Ka2 in the Coka-ray are separated by adjusting to extract only the Ka1, and the total width in half of the maximum (°) refracted by the Ka1-ray of the crystal plane (211) of the sample is measured . In addition, the total width at half the maximum is measured at a height that is half the height of the peak (peak top method). In addition, in relation to the total width at half the maximum derived from the equipment, the total width at half the maximum derived from the equipment is measured using a single crystal (ideal single crystal that does not have a total width at half the maximum) of LaB5 (lanthanum hexaboride), and the correction can be performed by subtracting the total width from half of the maximum derived from the equipment from the value actually measured.
[0090] The displacement acts as the weak hydrogen trapping site, the trapped hydrogen is able to diffuse again, so that the SSC resistance decreases. Consequently, it is preferable that the displacement density is low. When the total width at half the maximum meets Expression 1, the displacement density is considered to be suppressed, and thus diffusible hydrogen is difficult to accumulate in steel. Consequently, excellent SSC resistance can be obtained. On the other hand, when home
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28/70 total weight at half the maximum does not satisfy Expression 1, it is considered that the suppression of the displacement density is insufficient, and thus the SSC resistance is insufficient.
[0091] The lower limit of HW x C ^1/2 is not particularly limited. To preferably improve the SSC resistance, lower values of HW x C ^1/2 are preferred.
[0092] In addition, in low-alloy steel for tubular materials from oil fields according to the modality, it is preferable that the carbon content and the molybdenum content expressed in% by mass in the chemical composition satisfy a predetermined ratio to obtain preferably the effect of the aspect of the present invention.
RELATIONSHIP BETWEEN C CONTENT AND Mo CONTENT [0093] Preferably the chemical composition of low alloy steel for tubular materials from oil fields also satisfies Expression 2.
C x Mo> 0.6 (Expression 2) [0094] Here, in Expression 2, the content of C (% by mass) is replaced by the symbol of the element C and the content of Mo (% by mass) is replaced by the symbol of the Mo element.
[0095] When the C content and the Mo content satisfy Expression 2 and production is carried out under production conditions as described below, hexagonal M2C carbides are formed, and their number must be 5 particles / pm ² or more. Consequently, excellent SSC resistance can be obtained. More specifically, sufficient SSC strength can be obtained for the grade of 125 ksi or greater, and a high Kissc value can be obtained for the grade of 110 ksi or greater.
[0096] To also improve the SSC resistance, the relationship between the C content and the Mo ester is preferably C x Mo> 0.65, and more preferably C x Mo> 0.7.
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STRUCTURE [0097] As mentioned above, the structure of low alloy steel for tubular materials from oil fields according to the modality includes a mixed structure of tempered martensite and tempered bainite. More specifically, the structure of low-alloy steel for tubular oilfield materials includes mainly tempered martensite and tempered bainite, and may include precipitates such as carbides, nitrides and a fraction of residual austenite (the volume fraction of residual austenite for the total structure, in units of%) it can be 5% or less. This is because the residual austenite causes irregularity of resistance;
[0098] The fraction of residual austenite is measured by the X-ray diffraction method as follows. Specifically, samples are collected that include the central portion of the thickness of the steel plate produced or the steel pipe produced. The surface of the collected sample is chemically polished. X-ray diffraction is performed on the chemically polished surface by using CoKa-ray (Ka1) as an incident X-ray. The fraction of residual austenite is analyzed quantitatively from the integrated diffraction intensity of the crystal plane corresponding to the crystal plane (211), crystal plane (200), and crystal plane (110) of an α phase and the intensity of integrated diffraction of the crystal plane (220), the crystal plane (200) and the crystal plane (111) of austenite. [0099] In addition, when the C content is high like low alloy steel for tubular materials from oil fields according to the modality, the temper fracture due to the transformation into martensite tends to occur. As a method of suppressing the temper fracture, there is a method in which water cooling during tempering is temporarily interrupted for the low alloy steel structure for tubular oilfield materials to have a structure composed mainly of bainite. A considerable amount of carbides
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30/70 is formed during tempering. Carbides delay recovery from displacement during tempering. Therefore, in the case of the structure composed mainly of bainite, the displacement density increases, and so Expression 1 is not satisfied.
[00100] When the fraction of martensite in the structure after hardening is high, the displacement density decreases by tempering. At the moment, it is difficult to measure quantitatively this volume fraction of the martensite and the volume fraction of the bainite in the steel after hardening. However, the hardness of the steel after quenching (ie, of the material rapidly cooled) increases with an increase in the fraction of martensite in the steel. Consequently, when Rockwell hardness (HRC) on the C scale in the central portion of the thickness (central portion of the steel plate or steel tube thickness) of low-alloy steel for oilfield tubular materials after tempering and before tempering (i.e., the material rapidly cooled) preferably satisfies Expression 3 below, a sufficient fraction of the martensite is formed in the steel to decrease the displacement density by tempering.
Rockwell hardness (HRC)> 50 x C + 26 (Expression 3) [00101] For example, in steel where the C content is 0.6%, when Rockwell hardness (HRC) is 56 or more, the displacement is sufficiently recovered after tempering (that is, Expression 1 is satisfied), and the SSC resistance increases.
[00102] In low alloy steel for tubular materials from oil fields according to the modality, while satisfying the chemical composition mentioned above and the metallographic structure mentioned above, it is possible to obtain the important effect so that the flow limit and the SSC resistance are both excellent. Specifically, low-alloy steel for tubular materials from oil fields according to the modality, which satisfies both
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31/70 the chemical composition mentioned above and the metallographic structure mentioned above, has a yield limit of 758 MPa or more, and is excellent in SSC resistance containing the SSC resistance in the high pressure hydrogen sulfide environment, the SSC resistance in the case where the notch is applied and the like.
[00103] Next, a method of producing low-alloy steel for tubular materials from oil fields will be described in accordance with an embodiment of the invention. The production method according to the modality is for low alloy steel for tubular materials from oil fields mentioned above.
PRODUCTION METHOD [00104] In the production method of low alloy steel for tubular materials from oil fields according to the modality, a method of producing seamless steel tubes (tubular materials from low alloy oil fields) will typically be described .
[00105] The low alloy steel production method for oilfield tubular materials as configured includes a steelmaking process, a casting process, a roughing process, a hot work process, a rapid cooling and a tempering process.
[00106] As a steel production process, steel having the chemical composition described above is melted, and is refined by a conventional method. Subsequently, as a casting process, the molten steel is formed into a continuous casting material (casting) by a continuous casting method. The continuous casting material is, for example, a plate or a block. If not, the molten steel can be formed into a round bar by the continuous casting method. In addition, molten steel can be cast into an ingot by an ingot production method.
[00107] As needed, as a roughing process, the plate,
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32/70 block or ingot is hot-chopped to form a bar (bar for producing seamless steel pipe). The bar can be formed by hot rolling or hot forging.
[00108] As a hot work process, the bar obtained by continuous casting or hot roughing is worked hot to produce a steel material. In the modality, the shape of the steel material is that of a tube material. For example, in the hot work process, a Mannesmann process is performed as hot work to produce the tube material. The tube material can be produced by other working methods.
[00109] As a quick cooling process, the quenching is performed for the hot-worked steel material (tube material). Like quenching in the tempering process, for example, either the C10 cooling by a continuous cooling treatment or the C11 cooling including an isothermal treatment as shown in FIG. 3 can be adopted. In the invention, both the C10 temper by the continuous cooling treatment and the C11 temper including the isothermal treatment are defined as rapid cooling. In steel according to the modality in which the C content is high, when the pipe thickness is approximately 10 m or more and a common rapid cooling method is applied, the rapid cooling fracture tends to occur in the quench. Thus, the rapid cooling method is adopted as shown in FIG. 3. In addition, the Ms point in Fig. 3 represents the temperature at which martensite is started.
[00110] Even in any rapid cooling (quenching by continuous cooling treatment or quenching including isothermal treatment), it is preferable that the tempering temperature of the steel material (temperature of the surface of the steel material at the beginning of tempering) ) is 850 ° C to 920 ° C.
[00111] In addition, the temperature at which the transformation begins
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33/70 martensite (Ms point) varies depending on the chemical composition of the steel. The Ms point of each chemical composition can be estimated without a large margin of error by a typical estimated formula such as Expression 4 below, for example. In relation to the formula estimated below, elements that are not included in the chemical composition can be replaced by zero.
Ms (° C) = 521 - 353 x C - 22 x Si - 24.3 x Mn - 7.7 x Cu - 17.3 x Ni 17.7 x Cr - 25.8 x Mo (Expression 4) [00112 ] Hereinafter the tempering by continuous cooling treatment and cooling including isothermal treatment will be described in detail.
FAST COOLING BY CONTINUOUS COOLING TREATMENT IN THE FAST COOLING PROCESS [00113] In the case of cooling by the continuous cooling treatment, as shown in a C10 curve of FIG. 3, the steel material is cooled continuously from the temperature of the beginning of the quench, and the surface temperature of the steel material is decreased continuously. As a continuous cooling treatment, for example, a method of cooling the material by immersion in a water bath or an oil bath, or a method of cooling the material by pouring cooling water, or by cooling, can be applied. to air.
[00114] In the continuous cooling treatment, a time (passage time at point Ms) for which the temperature of the surface of the steel material reaches the temperature of start of transformation into martensite (point Ms) from the temperature of beginning of the quench , it is preferably 100 seconds to 600 seconds. When the passage time at point Ms is more than 600 seconds, it is difficult to obtain the hardness that satisfies Expression 3, and thus the fraction of martensite in the steel structure after tempering decreases. Therefore, Expression 1 is not
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34/70 satisfied, and thus an excellent SSC resistance cannot be obtained. [00115] In addition, when the passage time at the Ms point is greater than 600 seconds, the grain contour carbides are formed during cooling. It is a case in which grain-bound carbides are formed, carbides act as cores and grow during tempering, and C, Mo and the like in steel are consumed. Thus it is difficult to form hexagonal M2C carbides preferably. As a result, excellent SSC strength cannot be achieved.
[00116] On the other hand, when the passage time at point Ms is less than 100 seconds, the cooling fracture tends to occur during tempering. Thus, it is preferable that the passage time at point Ms is 100 seconds or more.
[00117] In a case where the steel material is a pipe material (steel pipe) and the quenching by continuous cooling treatment is performed, the cooling rate in a range where the temperature of an external surface of the pipe steel reaches 500 ° C from 800 ° C is defined as CR8-5 (° C / s). In a case where the amount of C in the tube material is approximately 0.6%, the CR8-5 cooling rate preferably satisfies Expression 5 below.
CR8-5 <2837 xt ^-2 , ² (Expression 5) [00118] Here, t represents the thickness (in units of mm) of the steel tube.
[00119] When the CR8-5 cooling rate satisfies expression 5, the occurrence of the rapid cooling fracture is preferably suppressed in the steel tube in which the quench by the continuous cooling treatment was performed. During cooling, there is a time difference in the occurrence of martensite transformation between the side of the outer surface and the side of the inner surface of the steel pipe. Therefore, it is considered that the residual stress that makes the fracture
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35/70 of cooling be generated in the steel tube. The residual stress derived from tempering can be obtained by analyzing the distribution of a finite element method (FEM - Finite Element Method). By comparing the value of the residual stress from the result of the FEM analysis and the cooling fracture behavior of the real steel tube, when the residual tensile stress of is 200 MPa or less, it must be confirmed that the cooling fracture steel tube of the mode is deleted.
[00120] With an increase in thickness 1 (mm) of the steel tube, the time difference in the occurrence of martensite transformation between the inner surface and the outer surface of the steel tube increases, and thus the residual tensile stress increases. As the cooling rate decreases, the time difference in the transformation of martensite described above decreases. Consequently, residual traction stress decreases, and thus the occurrence of a fracture on cooling is also suppressed.
[00121] FIG. 4 is a view illustrating the relationship between the thickness t (mm) of the steel tube and the cooling rate CRs-5 (° C / s) to suppress the cooling fracture during tempering in the continuous cooling treatment. Curve C4 in FIG. 4 represents the right side (= 2837 xt ^-2 , ² ) of Expression 5. Curve C4 represents the relationship between the cooling rate CR8-5 (° C / s) and the thickness t (mm) of the steel tube with which the residual tensile stress becomes 200 MPa.
[00122] And in relation to FIG. 4, the cooling fracture is suppressed on the smaller side of the C4 curve. On the other hand, the cooling fracture tends to occur on the upper side of the C4 curve. Consequently, the steel tube is preferably cooled during cooling so that the cooling rate satisfies Expression 5. In this particular case, it is possible to produce the seamless steel tube that does not have the cooling fracture defect or in which the occurrence of the fracture
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36/70 of cooling is suppressed, in the seamless steel tube having an outside diameter of 100 to 400 mm and a thickness of 5 to 100 mm. In addition, the value on the right side (= 2837 xt ^-2 ' ² ) of Expression 5 corresponds to a case in which the amount of C in the steel is approximately 0.6%. With an increase in C content, the upper limit of the cooling rate to suppress cooling fracture changes to a cooling rate that is less than that calculated on the right side of Expression 5. With a decrease in the amount of C increase , the upper limit of the cooling rate to suppress the cooling fracture changes to a cooling rate that is greater than that calculated by the right side of Expression 5.
[00123] Specifically, in the case where cooling by continuous cooling treatment is conducted in the cooling process, it is possible to improve the SSC resistance of low-alloy steel for tubular materials from oil fields by controlling the passage time through point Ms and it is possible to preferentially suppress the cooling fracture during production by estimating the preferable production conditions with the ratio of CR8-5 <2837 xt ^-2 ' ² .
[00124] Rapid cooling including isothermal treatment in quenching [00125] Quenching (curve C11) with isothermal treatment in FIG. 3 includes a first cooling treatment (initial cooling), an isothermal treatment, and a second cooling treatment (final cooling).
[00126] In the initial cooling, the steel material (tube material) after hot work is cooled from the temperature of the beginning of the rapid cooling to a temperature range of greater than the point Ms up to 300 ° C, and the cooling is interrupted in the temperature range greater than the Ms point up to 300 ° C. When the cooling stop temperature is greater than 300 ° C, the fraction of the bainite in the es
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37/70 steel structure increases excessively, and thus a large amount of carbides is formed. Therefore, displacement is difficult to recover during temper treatment, and displacement density is difficult to decrease. As a result, the hardness of the steel after cooling does not satisfy Expression 3, and thus Expression 1 is not satisfied. Therefore, excellent SSC resistance cannot be achieved.
[00127] In addition, when the cooling stop temperature is greater than 300 ° C, grain boundary carbides are formed, carbides act as nuclei and grow during tempering, and C, Mo and the like in steel are consumed . Thus, it is difficult to form the hexagonal M2C carbides preferably. As a result, excellent SWSC resistance cannot be achieved.
[00128] On the other hand, when the cooling stop temperature is point Ms or less, the cooling fracture tends to occur when the cooling rate is rapid. In addition, when the cooling stop temperature is Ms or less, the cooling substantially corresponds to the continuous cooling treatment.
[00129] In the isothermal treatment, the steel material after the initial cooling is maintained for a predetermined time in the temperature range of greater than the point Ms up to 300 ° C. It is sufficient that the steel material is kept within the temperature range described above in the isothermal treatment, and that the steel material is not limited to being kept at a constant temperature. A preferable retention time in isothermal treatment is 5 minutes to 60 seconds.
[00130] In the final cooling, the steel material after the isothermal treatment is cooled. Final cooling can be water cooling or air cooling. In other words, the rate of cooling during the final cooling is not particularly limited.
[00131] In the rapid cooling process included the treatment
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38/70 isothermal, the temperature (greater than the Ms point up to 300 ° C) of the isothermal treatment is lower than the temperature range in which the bainite transformation tends to occur. Therefore, the rapid cooling process including isothermal treatment is different from the ausrevention described in Unexamined Japanese Patent Application, First Publication No. 2006-265657.
[00132] From the point of view of controlling the cooling fracture, the isothermal treatment is carried out at a temperature higher than the point Ms and 300 ° C or less. In this case, the cooling rate of the initial cooling can be controlled to be large enough. Although a detailed mechanism is not clear, in this case, it is considered that a small amount of the bainite that precipitates during the isothermal treatment suppresses the occurrence of the rapid cooling fracture during the final cooling.
[00133] In a case where tempering with isothermal treatment is conducted, it is preferable that the cooling rate in the initial cooling is 0.7 ° C / s or more. When the cooling rate is less than 0.7 ° C / s, ferrite and perlite or a large amount of bainite can be formed. In addition, while the isothermal treatment is suitable in the case where cooling with the isothermal treatment is conducted, the upper limit of the cooling rate in the initial cooling is not particularly limited.
[00134] In addition, in the cooling process including quenching by continuous cooling treatment and quenching with isothermal treatment, when Rockwell hardness on the C scale in the central portion of the steel material thickness after the rapid cooling process and before the The tempering process is HRC, it is preferable that the steel material is cooled quickly under the condition that Rockwell HRC hardness meets Expression 3 below. When Rockwell HRC hardness meets Expression 3 below, a
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39/70 a sufficient fraction of martensite is formed in the steel to decrease the displacement density by tempering.
HRC> 50 x C + 26 (Expression 3)
COOLING PROCESS [00135] After the quenching is performed by the continuous cooling treatment or the quenching including the isothermal treatment, the quenching is performed for the steel material. The tempering temperature is adequately controlled according to the chemical composition of the steel material and the desired flow limit. In other words, the flow limit can be controlled to 758 MPa or more, and more preferably to 862 MPa or more by adjusting the tempering temperature.
[00136] The tempering temperature is preferably 680 ° C to the Aci point. The lower limit of the tempering temperature is more preferably 690 ° C, more preferably greater than 700 ° C, and even more preferably 710 ° C. While the tempering temperature is the Aci point or less, the hexagonal M2C carbides are preferably formed with an increase in the tempering temperature. The preferable tempering time is 10 minutes to 90 minutes for soaking.
[00137] In addition, the Aci point is the temperature at which the transformation of austenite begins during heating. The Aci point of each chemical composition can be estimated without a large margin of error by a typical estimated formula such as Expression 6 below, for example. In relation to the formula estimated below, elements that are not included can be replaced by zero in the chemical composition.
Ac (° C) = 750.8 - 26.6 x C + 17.6 x Si - 11.6 x Mn - 22.9 x Cu - 23 x Ni - 24.1 x Cr + 22.5 x Mo - 39.7 x V - 5.7 x Ti + 232.4 x Nb - 169.4 x Al - 894.7 x B (Expression 6)
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40/70 [00138] In a case where the chemical composition of the steel material meets Expression 2 mentioned above and tempering is performed at the preferable tempering temperature described above, 5 particles / pm ² or more of hexagonal M2C carbides having a size grain of 1 nm or more precipitate on the steel, and thus the SSC resistance increases.
[00139] From the processes described above, low alloy steels are produced for oilfield materials (seamless steel tubes) that are both excellent in yield strength and SSC resistance. Especially, through the wide control of the tempering process and the tempering process, it is possible to control the formation of hexagonal M2C carbides and the displacement density control simultaneously.
[00140] In the production method described above according to the modality, the tempering process is performed after the hot work process. However, a normalization process to normalize the steel material (tempering) can be carried out between the hot working process and the tempering process. Specifically, the steel material (tube material) after the hot working process is maintained for a predetermined time at a high temperature of the point Ac3 or higher, and then the steel material is cooled. The holding temperature is preferably 900 ° C to 920 ° C. The retention time is, for example, 5 minutes to 60 minutes. In addition, the point Ac3 is a temperature at which the transformation of austenite ends during heating.
[00141] Commonly, in the normalization process, the steel material after the hot working process is cooled to room temperature, and then the steel material is heated to the point Ac3 or higher. However, the normalization process can be performed by directly retaining the steel material after the
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41/70 hot work at a temperature of point AC3 or higher. In addition, the Ar3 point is a temperature at which the transformation of the ferrite begins during cooling.
[00142] When the normalization process is performed, the crystal grain of the steel is refined. Specifically, after the quench in which the normalization process is performed, (ie on the material as it rapidly cooled), the grain size of the previous austenite becomes 10 or more what is defined in ASTM E112. By refining the crystal grain, the SSC strength is also improved.
[00143] In the production method above, the method of producing the seamless steel tube is explained in relation to the steel material such as tube material or steel tube. However, the shape of the steel material is not particularly limited. The steel material can be a plate, a steel bar or a wire rod.
[00144] In addition, in the production method described above, steel material having a chemical composition that satisfies Expression 2 is used and the tempering temperature is specified to form 5 particles / pm ² or more of the hexagonal M2C carbides having size grain of 1 nm more in steel. However, 5 particles / pm ² or more of hexagonal M2C having a grain size of 1 nm or more can be precipitated on steel by different production conditions. EXAMPLE 1 [00145] Ingots were produced from steel A to steel Z and steel AA to steel AG which have the chemical compositions shown in Table 1 and Table 2. In Table 2, the Ms points calculated from Expression 4 are shown and the Aci points calculated from the Expression
6. In addition, in the Tables, the underlined values indicate outside the range of the present invention, and arm values indicate that no connecting elements were intentionally added.
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TABLE 1
KIND OFSTEEL CHEMICAL COMPOSITION (% by mass, balance consisting of Fe and impurities) Ç Si Mn P s Al Mo O N THE 0.50 0.20 0.44 0.009 0.001 0.034 1.47 0.001 0.0036 B 0.49 0.20 0.44 0.008 0.001 0.033 1.97 0.002 0.0036 Ç 0.50 0.20 0.45 0.009 0.001 0.031 2.48 0.001 0.0031 D 0.49 0.20 0.45 0.009 0.001 0.032 2.95 0.001 0.0033 AND 0.50 0.20 0.44 0.008 0.001 0.032 3.44 0.001 0.0033 F 0.51 0.20 0.45 0.009 0.001 0.034 3.97 0.001 0.0033 G 0.61 0.21 0.46 0.008 0.001 0.037 2.51 0.001 0.0140 H 0.40 0.19 0.44 0.009 0.001 0.031 1.57 0.001 0.0040 I 0.39 0.20 0.44 0.009 0.001 0.033 2.02 0.001 0.0035 J 0.39 0.20 0.44 0.008 0.001 0.031 2.43 0.001 0.0040 K 0.50 0.20 0.44 0.008 0.001 0.034 1.50 0.001 0.0038 L 0.50 0.20 0.43 0.008 0.001 0.033 1.51 0.001 0.0035 M 0.60 0.15 0.60 0.010 0.001 0.029 1.15 0.001 0.0030 N 0.61 0.21 0.38 0.008 0.001 0.030 2.01 0.001 0.0041 O 0.60 0.20 0.45 0.009 0.001 0.034 2.09 0.001 0.0045 P 0.59 0.20 0.44 0.009 0.001 0.030 1.51 0.001 0.0040 Q 0.62 0.39 0.50 0.008 0.001 0.029 2.51 0.002 0.0034 R 0.56 0.21 0.40 0.009 0.001 0.030 1.10 0.001 0.0030 s 0.71 0.45 0.45 0.008 0.001 0.029 2.48 0.001 0.0041 T 0.36 0.19 0.85 0.009 0.001 0.034 1.90 0.001 0.0039
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TABLE 1 -continuation-
KIND OFSTEEL CHEMICAL COMPOSITION (% by mass, balance consisting of Fe and impurities) Ç Si Mn P s Al Mo O N U 0.50 0.21 0.45 0.009 0.001 0.029 1.30 0.001 0.0040 V 0.27 0.20 0.45 0.013 0.003 0.028 2.47 0.001 0.0043 W 0.59 0.19 1.20 0.009 0.001 0.031 2.51 0.001 0.0044 X 0.60 0.40 0.55 0.030 0.001 0.029 2.09 0.001 0.0040 Y 0.59 0.45 0.74 0.010 0.011 0.030 2.10 0.001 0.0040 Z 0.49 0.20 0.44 0.008 0.001 0.033 0.70 0.001 0.0034 AA 0.50 0.20 0.45 0.008 0.001 0.033 1.02 0.001 0.0032 AB 0.39 0.20 0.43 0.008 0.001 0.031 0.69 0.001 0.0045 B.C 0.40 0.20 0.44 0.008 0.001 0.032 0.99 0.001 0.0039 AD 0.27 0.20 0.45 0.011 0.002 0.036 1.92 0.001 0.0038 AE 0.58 0.19 0.44 0.012 0.0022.51 0.011 0.0045 AF 0.50 0.36 0.61 0.007 0.002 0.030 1.13 0.001 0.0032 AG 0.49 0.21 0.46 0.010 0.001 0.033 1.10 0.001 0.0041
* In the Table, underlined values indicate outside the range of the present invention
0Z / S17 * In the Table, blanks indicate that no alloying elements were intentionally added
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TABLE 2
KIND OFSTEEL CHEMICAL COMPOSITION F2 Calculated Ms Point(Ç) Calculated Ac1(Ç) (% by mass, balance consisting of Fe and impurities) Cr V Nb You Zr Here B THE0.10 0.029 0.010 0.74 291 766 B0.10 0.029 0.010 0.97 282 778 Ç0.10 0.028 0.008 1.24 265 789 D0.10 0.027 0.010 1.45 257 799 AND0.10 0.027 0.010 1.72 241 810 F0.10 0.029 0.010 2.02 223 822 G0.10 0.017 0.016 1.53 225 783 H0.10 0.026 0.015 0.63 324 770 I0.10 0.027 0.015 0.79 316 781 J0.10 0.026 0.015 0.95 306 790 K 0.20 0.10 0.028 0.016 0.75 287 771 L 0.50 0.10 0.027 0.017 0.76 282 779 M 0.69 262 751 N 0.20 1.23 236 779 O0.051.25 240 772 P 0.0290.030 0.89 259 769 Q0.00221.56 217 787 R 0.0011 0.62 281 754 s 0.030 0.015 1.76 186 792 T0.25 0.035 0.010 0.68 320 770
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TABLE 2 -CONTINUATION-
KIND OFSTEEL CHEMICAL COMPOSITION F2 Calculated Ms Point(Ç) Calculated Ac1(Ç) (% by mass, balance consisting of Fe and impurities) Cr V Nb You Zr Here B U0.20 0.030 0.011 0.65 295 759 V0.10 0.031 0.021 0.0010 0.67 347 795 W 0.033 0.010 1.48 215 783 X 0.031 0.011 1.25 233 785 Y 0.029 0.010 1.24 231 783 Z0.10 0.030 0.010 0.34 315 749 AA0.10 0.031 0.011 0.51 303 756 AB0.10 0.026 0.015 0.27 351 751 B.C0.10 0.028 0.016 0.40 339 758 AD0.10 0.028 0.014 0.0010 0.52 361 781 AE 0.025 0.010 1.46 237 796 AF0.10 0.015 0.011 0.57 293 757 AG 0.54 304 755
* In the Table, underlined values indicate outside the range of the present invention
45/70 * In the Table, blank spaces indicate that no connection element was added intentionally.
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46/70 [00146] The value that is obtained by Expression 7 below is shown in column F2 in Table 2.
F2 = C x Mo (Expression 7) [00147] In summary, F2 is the left side of Expression 2.
[00148] All chemical compositions from steel A to steel U were within the range of the invention, and F2 satisfied Expression 2. On the other hand, in steel V to steel Z and steel AB to steel AE, at least one of the levels of the elements cut out of the range the inventions. The chemical compositions of AA steel, AF steel, and AG steel were within the range of the invention, but did not satisfy Expression 2.
[00149] The weight of the respective ingots was 30 kg to 150 kg. Blocks were taken from the respective ingots. The blocks were heated to 1250 ° C. The heated blocks were hot forged and hot rolled to produce steel materials (sheet materials) having a thickness of 15 mm to 25 mm.
[00150] The quenching and tempering treatments, or the quenching and tempering treatments after the normalization treatment were performed using the produced plate materials. And the flow limit of the plate materials was controlled for the grade 110 ksi (758 Pa or more) and for the grade 125 ksi (862 MPa more).
[00151] In the normalization treatment, the soak was performed for 10 minutes at a temperature (920 ° C) of the point Ac3 or greater, and then the cooling was conducted in the air. In addition, tempering and tempering were carried out as follows.
HARDENING [00152] The tempering start temperature during tempering was controlled over a range of 850 ° C to 920 ° C.
TEMPERING AND CONTINUOUS COOLING TREATMENT [00153] In the case of tempering by continuous cooling treatment, after each plate material has been heated
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47/70 until the tempering start temperature, the passage time at the point Ms (time taken from the temperature at the beginning of the tempering to the temperature at which martensite starts to transform (point Ms)) Tcc (seconds) was controlled by cooling by water spray, mist cooling or air cooling.
COOLING INCLUDING ISOTHERMAL TREATMENT [00154] In a case of tempering including the isothermal treatment, the first cooling treatment (initial cooling) was performed at a cooling rate of 0.7 ° C / s or more by cooling with a bath of salt or water cooling. The ATic cooling stop temperature (° C) of the initial cooling was changed by pulling the sheet material up in the middle of the cooling. The retention (isothermal treatment) was performed at the ATic cooling stop temperature for 25 minutes to 40 minutes, and then the water cooling (second cooling treatment (final cooling)) was performed up to a common temperature.
TESTING FOR QUICKLY COOLED MATERIAL [00155] The following tests were performed for plate material after tempering (hereinafter referred to as rapidly cooled material).
QUICKLY COOLED MATERIAL HARDNESS TEST [00156] The hardness of the cooled material was quickly measured by the following method. The cooled material was quickly cut along the thickness direction. Then the Rockwell hardness (HRC) on the C scale in the central portion of the thickness in the cross section was obtained based on the JIS (Japanese Industrial Standard) G 0202. Specifically, the Rockwell HRC hardness was obtained at three arbitrary points in the central portion of the thickness of the transversal section. An average of Rockwell hardness (HRC) obtained at the three points was defined as the hardness of a corresponding mark.
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PREVIOUS AUSTENITE GRAIN SIZE TEST [00157] In addition, a grain size test of the previous austenite was performed using the rapidly cooled material. Specifically, the cooled material was cut along the thickness direction. In addition, the cut sheet material was embedded in resin and polished, and then the cross section was etched with picric acid. The etched cross section was observed, and the grain size of the previous austenite was determined based on ASTM E112. TEMPERING [00158] Tempering was performed for plate materials after tempering. The flow limit of the respective material sheets was controlled for the grade 110 ksi (758 MPa or more) and 125 ksi (862 MPa or more) by controlling the tempering temperature (° C) and the tempering time (minutes) .
MATERIAL EVALUATION TEST PLATE AFTER COVERING.
[00159] The following evaluation tests were performed on the plate materials that were subjected to tempering and tempering.
TEST OF TOTAL WIDTH MEASUREMENT IN HALF MAXIMUM AND TEST OF MEASUREMENT OF RESIDUAL AUSTENITE FRACTION [00160] Test specimens were taken from the plate materials after quenching. The surface of each test specimen was polished with paper. The finer size of the paper was used for polishing. After the surface of the test specimen was polished with No. 1200 paper, a work-hardened layer that was formed by polishing the surface of the test specimen was removed by immersing the test specimen in hydrogen peroxide that contained a small amount of hydrofluoric acid and was kept at a normal temperature. The X-ray diffraction test was performed for the test specimen from which the layer hardened in the
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49/70 work was removed under conditions of 30 kV and 100 mA using CoKa-ray (Ka1 having a wavelength of 1.7889 A) to obtain the total width at half the maximum (*) of a diffraction peak of the crystal plane corresponding to the crystal plane (211) of the α phase of the test specimen.
[00161] Specifically, Ka1 and Ka2 in CoKa-ray were separated adjusting to extract only Ka1, and the total width was obtained in half of the maximum (*) diffracted by the Ka1-ray of α-Fe of the crystal plane (211) of the test specimens. In addition, the total width at half the maximum was measured at a height that was half the height of the peak (peak-top method). In addition, in relation to the total width at half the maximum derived from an equipment, the total width at half the maximum derived from the equipment was measured using a single crystal (ideal single crystal that does not have the total width at half the maximum) of LaB6 (lanthanum hexaboride), and the correction was performed by subtracting the total width in half of the maximum derived from the equipment from the value actually measured.
[00162] In addition, the residual austenite fraction (volume fraction (%) of the residual austenite for the total) was measured by the X-ray method described above. Specifically, the test specimen was taken, which includes the central portion of the thickness of the steel material. The surface of the taken test specimen was chemically polished. X-ray diffraction was performed on the chemically polished surface using CoKa-ray (Ka1 having a wavelength of 1.7889 A) as an incident ray. The fraction of residual austenite was analyzed quantitatively from the integrated diffraction intensity of the crystal plane corresponding to the crystal plane (211) to the crystal plane (200), and to the crystal plane (110) of the α phase, and the intensity integrated diffraction of the crystal plane (220), the crystal plane (200), and the crystal plane (111) of austenite.
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FLOW LIMIT TEST [00163] From the respective plates after tempering, specimen round bars of tensile test having a parallel portion with an outside diameter of 6 mm and a length of 40 mm were taken so that the direction of pull it must be the longitudinal direction or the lamination direction of the sheet material. A tensile test was performed using the tensile test specimen at a common temperature (25 ° C) to obtain the yield limit (stress test 0.2%, in MPa units).
SSC STRENGTH TEST [00164] In the SSC strength test, a constant load tensile test and an autoclave test were performed using sheet material having a yield limit of 125 ksi (862 MPa) or more.
CONSTANT TRACTION LOAD TEST [00165] From the respective plate materials, specimens were drawn round bar of tensile test having a parallel portion in which the direction of traction should be the longitudinal direction or the lamination direction of the plate material. The outside diameter of the parallel portion was 6.35 mm, and its length was 25.4 mm. The constant load traction test was performed in the test bath at a common temperature (25 ° C) based on NACE TM0177 Method A. As a test bath, bath A was used. Bath A was an aqueous solution of 5 % NaCl and 0.5% CH3COOH, which was maintained at a common temperature and in which the 1 atm hydrogen sulfide gas was saturated.
[00166] Each of the test specimens was immersed in bath A. A constant load that was 90% of an actual yield limit (yield limit of the respective marks) was applied to the test specimen in bath A. The occurrence of fracture was confirmed in
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51/70 test specimen after 720 hours. The plate materials in which the fracture did not occur were considered as plate material having excellent SSC resistance.
AUTOCLAVE TEST [00167] Considering that the steel material would be used under a well environment where the hydrogen sulfide pressure would be 1 atm or higher, which would be recently required, an autoclave test was performed using a B bath. Bath B was a 5% aqueous solution of NaCl in which the 10 atm hydrogen sulfide was saturated. A specific test method was as follows.
[00168] Four-point bend test specimens having 2 mm x 10 mm x 75 mm were taken from the respective plate materials. A stress of 90% of an actual yield limit (yield limit of the respective brands) was applied to four-point folding specimens taken using a four-point folding template based on ASTM G39. The four-point fold test specimen to which the stress was applied was placed in an autoclave. After the four-point folding test specimen was placed, the degassed aqueous solution of 5% NaCl was filled into the autoclave. Thereafter, 10 atm hydrogen sulfide was filled there. By the procedure described above, bath B was prepared in the autoclave, and the four-point folding test specimen was immersed in bath B. The occurrence of fracture was confirmed visually in the test specimen after 720 hours since filling with hydrogen sulfide. 10 atm. Plate materials in which the fracture did not occur were judged to be plate material having excellent SSC resistance. In addition, a pressure inside the autoclave during the test was controlled to be constantly 10 atm.
DCB TEST
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52/70 [00169] Test specimens DCB (Double Cantilever Radius) having a thickness of 10 mm, a width of 25 mm, and a length of 100 mm were taken from the plate materials having a yield limit of 110 ksi (758 MPa ) or more. The DCB test was performed using the DCB test specimens taken based on NACER TM0177 Method D. As the test bath, bath B was used. Each of the DCB test specimens was immersed in bath B for 336 hours. After 336 hours, the length of fracture propagation that occurred in the DCB test specimen was measured. The Kissc stress intensity factor (ksi ^ in) was obtained based on the measured length of the fracture propagation. Plate materials in which the Kissc stress intensity factor (ksi ^ in) was 25 ksi ^ in or more were judged as plate materials having excellent SSC resistance.
RESISTANCE TEST RESULT SS [00170] Production conditions and results of the SSC resistance test are shown in Tables 3 to 6.
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TABLE 3
BRANDS KIND OFSTEEL Ç(% in large scale) NORMALIZATION COOLING METHOD CBT(s) ATIC(° C) HRC HARDNESS F3 GRAIN SIZE 1 THE 0.50CC 10059.9 51.0 9.5 2 THE 0.50CC 10059.6 51.0 9.2 3 THE 0.50 Done CC 10060.3 51.0 11.0 4 THE 0.50 Done CC 10060.2 51.0 11.0 5 B 0.49CC 10059.8 50.5 9.5 6 B 0.49CC 10059.5 50.5 9.3 7 B 0.49 Done CC 10060.0 50.5 11.1 8 B 0.49 Done CC 10059.8 50.5 10.8 9 Ç 0.50CC 10058.7 51.0 9.6 10 Ç 0.50CC 10059.1 51.0 9.4 11 Ç 0.50 Done CC 10059.2 51.0 10.8 12 Ç 0.50 Done CC 10059.1 51.0 11.0 13 D 0.49CC 10058.3 50.5 9.3 14 D 0.49CC 10057.6 50.5 9.6 15 D 0.49 Done CC 10057.9 50.5 11.2 16 D 0.49 Done CC 10058.0 50.5 10.5 17 AND 0.50CC 10057.9 51.0 9.8 18 AND 0.50CC 10058.2 51.0 9.6
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TABLE 3 -continuation-
BRANDS KIND OFSTEEL C (% by mass) NORMALIZATION COOLING METHOD ω O o ATIC (° C) HRC HARDNESS F3 GRAIN SIZE 19 AND 0.50 Done CC 10057.7 51.0 11.0 20 AND 0.50 Done CC 10057.6 51.0 11.2 21 F 0.51CC 30057.0 51.5 9.5 22 F 0.51CC 30057.3 51.5 9.8 23 F 0.51 Done CC 30057.2 51.5 10.9 24 F 0.51 Done CC 30057.2 51.5 10.8 25 G 0.61CC 60061.0 56.5 9.3 26 G 0.61 Done CC 60062.5 56.5 10.9 27 G 0.61 Done CC 60060.5 56.5 11.0 28 G 0.61 Done CC 60062.0 56.5 11.0 29 G 0.61IC250 60.5 56.5 9.5 30 G 0.61IC250 61.0 56.5 9.5 31 H 0.40CC 10054.9 46.0 9.5 32 H 0.40 Done CC 10055.1 46.0 10.6 33 H 0.40 Done CC 10055.6 46.0 10.7 34 I 0.40CC 10048.8 46.0 9.5 35 I 0.40 Done CC 10051.0 46.0 11.1
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TABLE 4
BRANDS KIND OFSTEEL C (% by mass) NORMALIZATION COOLING METHOD CBT (sec.) ATIC(° C) HRC HARDNESS F 3 GRAIN SIZE 36 I 0.40 Done CC 10052.5 46.0 11.0 37 J 0.40CC 10052.8 46.0 9.4 38 J 0.40 Done CC 10053.0 46.0 11.0 39 J 0.40 Done CC 10052.6 46.0 11.2 40 K 0.50CC 10060.2 51.0 9.3 41 K 0.50 Done CC 10060.3 51.0 10.8 42 L 0.50 Done CC 10060.4 51.0 10.6 43 M 0.60CC 60058.5 56.0 8.6 44 N 0.61CC 60059.5 56.5 8.8 45 O 0.60CC 60060.2 56.0 8.5 46 P 0.59CC 60058.0 55.5 9.2 47 Q 0.62CC 60061.0 57.0 8.8 48 R 0.56CC 30057.0 54.0 8.7 49 s 0.71IC250 63.0 61.5 9.5 50 T 0.36CC 10051.0 44.0 9.6 51 U 0.50CC 10058.0 51.0 9.5 52 G 0.61IC250 62.5 56.5 9.5 53 G 0.61IC300 62.0 56.5 9.3 54 THE 0.50CC 100048.0 51.0 9.4 55 G 0.61CC 100053.5 56.5 9.5 56 G 0.61IC400 52.0 56.5 9.4
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TABLE 4 - continued.
BRANDS KIND OFSTEEL Ç(% in large scale) NORMALIZATION COOLING METHOD CBT (sec.) ATIC(° C) HRC HARDNESS F 3 GRAIN SIZE 57 M 0.60CC 100051.5 56.0 9.5 58 J 0.40CC 100042.0 46.0 9.3 59 V 0.27CC 10049.5 39.5 9.5 60 W 0.59CC 60058.5 55.5 9.6 61 X 0.60CC 60060.0 56.0 9.2 62 Y 0.59CC 60061.0 55.5 9.7 63 Z 0.49CC 10058.7 50.5 9.6 64 AA 0.50CC 10059.8 51.0 9.5 65 AB 0.40CC 10053.0 46.0 9.4 66 B.C 0.40CC 10054.6 46.0 9.5 67 AD 0.27CC 10048.2 39.5 9.3 68 AE 0.58CC 60059.0 55.0 9.4 69 AF 0.50CC 60059.5 51.0 9.6 70 AG 0.49CC 60059.0 50.5 9.5
* In the Table, underlined values indicate outside the range of the present invention
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TABLE 5
BRANDS KIND OFSTEEL REFERENCE HW(°) F1 M2C (pieces / pm ² ) YS (MPa) SSC TEST TEMPERATU-RA (° C) TIME (min.) SHOWERTHE BATH B 1 THE 710 30 0.41 0.29 20 912 none none 2 THE 720 30 0.40 0.28 20 896 none none 3 THE 700 30 0.44 0.31 10 923 none none 4 THE 710 30 0.40 0.28 20 890 none none 5 B 710 30 0.42 0.29 30 915 none none 6 B 720 30 0.38 0.27 20 878 none none 7 B 700 30 0.45 0.32 20 938 none none 8 B 710 30 0.38 0.27 20 917 none none 9 Ç 710 30 0.40 0.28 40 912 none none 10 Ç 720 30 0.36 0.25 30 880 none none 11 Ç 700 30 0.42 0.30 40 946 none none 12 Ç 710 30 0.38 0.27 40 917 none none 13 D 710 30 0.36 0.25 40 903 none none 14 D 720 30 0.33 0.23 60 882 none none 15 D 700 30 0.45 0.32 40 947 none none 16 D 710 30 0.41 0.29 50 923 none none 17 AND 710 30 0.38 0.27 50 906 none none 18 AND 720 30 0.31 0.22 40 879 none none
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TABLE 5 -continuation.
BRANDS KIND OFSTEEL REFERENCE HW(°) F1 M2C (pieces / pm ² ) YS (MPa) SSC TEST TEMPERATURE (° C) TIME (min.) SHOWERTHE BATH B 19 AND 700 30 0.42 0.30 50 928 none none 20 AND 710 30 0.35 0.25 50 893 none none 21 F 710 30 0.53 0.38 50 921 none none 22 F 720 30 0.47 0.34 40 899 none none 23 F 700 30 0.49 0.35 50 932 none none 24 F 710 30 0.45 0.32 50 929 none none 25 G 720 30 0.35 0.27 50 916 none none 26 G 700 30 0.32 0.25 40 919 none none 27 G 710 30 0.40 0.31 50 968 none none 28 G 720 30 0.20 0.16 60 924 none none 29 G 710 30 0.32 0.25 50 940 none none 30 G 720 30 0.40 0.31 40 947 none none 31 H 700 30 0.55 0.35 10 880 none none 32 H 700 30 0.50 0.32 20 918 none none 33 H 710 30 0.45 0.28 10 899 none none 34 I 700 30 0.40 0.25 40 890 none none 35 I 700 30 0.31 0.20 40 885 none none
58/70
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TABLE 6
BRANDS KIND OFSTEEL REFERENCE HW(°) F1 M2C (pieces / pm ² ) YS (MPa) SSC test TEMPERATURE(° C) TIME (min.) SHOWERTHE BATH B 36 I 710 30 0.46 0.29 50 893 none none 37 J 700 30 0.51 0.32 50 895 none none 38 J 700 30 0.45 0.28 40 885 none none 39 J 710 30 0.35 0.22 40 864 none none 40 K 700 30 0.38 0.27 10 910 none none 41 K 700 30 0.45 0.32 20 934 none none 42 L 710 30 0.42 0.30 30 936 none none 43 M 680 60 0.40 0.31 10 930 none none 44 N 700 60 0.38 0.30 30 928 none none 45 O 710 30 0.35 0.27 30 923 none none 46 P 700 30 0.28 0.22 20 928 none none 47 Q 710 30 0.40 0.31 40 922 none none 48 R 700 60 0.30 0.22 10 921 none none 49 s 710 30 0.45 0.38 30 918 none none 50 T 680 60 0.50 0.30 30 875 none none 51 U 700 30 0.37 0.26 20 915 none none 52 G 710 30 0.38 0.30 40 930 none none 53 G 710 30 0.40 0.31 40 925 none none
59/70
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TABLE 6 -continuation.
BRANDS KIND OFSTEEL REFERENCE HW(°) F1 M2C (pieces / pm ² ) YS (MPa) SSC test TEMPERATURE(° C) TIME(min.) BATH A BATH B 54 THE 640 30 0.56 0.40 0 879 Observed Obsessed 55 G 630 30 0.51 0.40 0 868 Observed Observed 56 G 620 30 0.52 0.41 0 868 Observed Observed 57 M 600 30 0.55 0.43 0 870 Observed Observed 58 J 600 30 0.65 0.41 0 888 Observed Observed 59 V 680 30 0.55 0.29 10 870 Observed Observed 60 W 700 30 0.42 0.32 30 886 Observed Observed 61 X 710 30 0.38 0.29 40 872 Observed Observed 62 Y 700 30 0.44 0.34 30 889 Observed Observed 63 Z 710 30 0.50 0.35 0 870 Observed Observed 64 AA 700 30 0.48 0.34 0 893 Observed Observed 65 AB 690 30 0.58 0.37 0 870 Observed Observed 66 B.C 690 30 0.55 0.35 0 890 Observed Observed 67 AD 690 30 0.53 0.28 0 877 Observed Observed 68 AE 710 30 0.45 0.34 30 880 Observed Observed 69 AF 700 30 0.52 0.37 0 895 Observed Observed 70 AG 700 30 0.52 0.36 0 890 Observed Observed
* In the Table, underlined values indicate outside the range of the present invention
60/70
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61/70 [00171] Done in a normalization column in Table 3 and Table 4 indicates that the normalization treatment was performed for the steel material of the corresponding brand. CC in a cooling method column indicates that the quench by the continuous cooling treatment was performed for the steel of the corresponding brand. IC indicates that the quench including the isothermal treatment was carried out for the steel of the corresponding brand. In a Tcc column, the passage time at the point Ms (seconds) in the continuous cooling treatment is shown. In an ATic column, the cooling stop temperature (° C) of the initial quench cooling including isothermal treatment is shown. In an HRC hardness column, Rockwell hardness (HRC) of the corresponding mark is shown. In a grain size column, the grain size of the previous austenite of the corresponding mark is shown. In a F3 column, the value F3 (= 50C + 26) is shown, which is a value on the right side of Expression 3. In a temperature column and a time column of a tempering column in Table 5 and Table 6, they are shown, respectively , the tempering temperature (° C) and the tempering time (minutes) of the corresponding mark. In an HW column, the total width is shown at half the maximum (°) of the corresponding mark. In column F1, F1 (= HW x C ^1/2 ) is shown, which is the left side of Expression 1. In an M2C column, the number (parts / pm ² ) of hexagonal M2C carbides is shown. In a YS column, the yield limit (MPa) of the corresponding mark is shown.
[00172] An SSC test column shows the results of the SSC resistance test in bath A and bath B. None indicates that the fracture did not occur. Observed indicates that the fracture occurred. [00173] In addition, the fraction of residual austenite from all brands 1 to 70 was 0%.
[00174] In relation to Table 3 to Table 6, it can be seen that all
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62/70 of the chemical compositions of the steel materials of brands 1 to 53 were within the chemical composition range of low alloy steel for tubular oilfield products of the invention. In addition, the F1 value was 0.38 or less, and met Expression 1 on steel materials from brands 1 to 53. In addition, the number of M2C hexagonal carbides having a grain size (equivalent circle diameter) of 1 nm or more was 5 particles / pm ² or more in steel materials from brands 1 to 53. In addition, the average aspect ratio of grain boundary carbides was 3 or less in steel materials from brands 1 to 53 53. Therefore, the fracture was not observed in the SSC strength test in both bath A and bath B in steel materials from brands 1 to 53.
[00175] In addition, the grain size of the anterior austenite of the marks (3, 4, 7, 8, 11, 12, 15, 16, 19, 20, 23, 24, 26-28, 32, 33, 35, 36, 38, 39, 41 and 42) in which the normalization treatment was performed was 10 or more, and its grains were refined compared to the brands in which the normalization treatment was not performed using the same type of steel ( for example, stretcher '1 or similar compared to brand 4).
[00176] On the other hand, in marks 54, 55, 57 and 58, the chemical composition was within the range of the invention and Expression 2 was satisfied, but the passage time at the point Ms Tcc in the temper by the continuous cooling treatment exceeded 600 seconds. In addition, the tempering temperature was less than 680 ° C. Therefore, Rockwell hardness was less than the F3 value and did not satisfy Expression 3 in the rapidly cooled material, and the F1 value exceeded 0.38 and did not satisfy Expression 1. In addition, the number of hexagonal M2C carbides having grain size 1 nm or more was less than 5 particles / pm ² . Consequently, at marks 54, 55 57 and 58, the fracture was observed in the SSC resistance test of both bath A and
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63/70 bath B. In addition, steels that have been quenched at 720 ° C for 30 minutes have been prepared using steels that have been rapidly cooled by the same conditions as marks 54, 55, 57 and 58. However, the limit steel flow was not 758 MPa or more, so other evaluations were not conducted.
[00177] In a 56 mark, the chemical composition was within the range of the invention and Expression 2 was satisfied. However, the stop temperature of ATic cooling at quenching including isothermal treatment was greater than 300 ° C. In addition, the tempering temperature was less than 680 ° C. Therefore, Rockwell hardness did not satisfy Expression 3 in the rapidly cooled material, and the F1 value exceeded 0.38 and did not satisfy Expression 1. In addition, the number of hexagonal M2C carbides having a grain size of 1 nm or more was less than 5 particles / pm ² . Consequently, at mark 56, the fracture was observed in the SSC resistance test of both bath A and bath B.
[00178] In a 59 mark, the C content was less than the lower limit of the C content of the invention. Therefore, the fracture was observed in the SSC strength test of both bath A and bath B. It is considered that the C content is insufficient, and thus the grain boundary carbides are not sufficiently coalesced.
[00179] In a 60 mark, the M content exceeded the upper limit of the invention. In a 61 mark, the P content exceeded the upper limit of the invention. In a 62 mark, the S content exceeded the upper limit of the invention. Therefore, the fracture was observed in the SSC resistance test in both bath A and bath B. It is considered that an excessive content of Mn, P and S segregated at the grain edges, and thus the SSC strength decreased.
[00180] In brands 63, 65 and 66, the Mo content was less than the lower limit of the invention. Therefore, the number of hexago M2C carbides
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64/70 nals having a grain size of 1 nm or more was less than 5 particles / pm ² . Therefore, in marks 63, 65 and 66, the fracture was observed in the SSC resistance tests in both bath A and bath B.
[00181] In brands 64, 69 and 70, the chemical composition was within the range of the invention, but Expression 2 was not satisfied. In addition, the number of hexagonal M2C carbides having a grain size of 1 nm or more was less than 5 particles / pm ² . Therefore, in marks 64, 69 and 70, the fracture was observed in the SSC strength test in both bath A and bath B.
[00182] In a 67 mark, the C content was less than the lower limit of the invention and Expression 2 was not satisfied. Therefore, the number of hexagonal M2C carbides having a grain size of 1 nm or more was less than 5 particles / pm ² . Therefore, the fracture was observed in the SSC resistance test in both bath A and bath B.
[00183] In mark 68, Al was not included in the steel material and the O content exceeded the upper limit of the invention. Therefore, the fracture was observed in the SSC resistance test in both bath A and bath B.
DCB TEST RESULTS [00184] The production conditions and results of the DCB test are shown in Table 7 and Table 8. In addition, the indication method and abbreviations in Table 7 and Table 8 correspond to Table 3 to Table 6.
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TABLE 7
BRANDS KIND OFSTEEL Ç(% in large scale) NORMALIZATION COOLING METHOD CBT (s.) ATI C(° C) HRC HARDNESS F 3 SIZE OFGRAIN 71 THE 0.50CC 10059.9 51.0 9.5 72 B 0.49CC 10059.8 50.5 9.5 73 Ç 0.50CC 10058.7 51.0 9.6 74 D 0.49CC 10058.3 50.5 9.3 75 AND 0.50CC 10057.9 51.0 9.8 76 F 0.51CC 30057.0 51.5 9.5 77 G 0.61CC 60061.0 56.5 9.3 78 H 0.40 Done CC 10054.9 46.0 10.9 79 I 0.40CC 10048.8 46.0 9.5 80 J 0.40CC 10052.8 46.0 9.4 81 K 0.50CC 10060.2 51.0 9.3 82 L 0.50 Done CC 10060.4 51.0 10.6 83 M 0.60CC 60058.5 56.0 8.6 84 N 0.61CC 60059.5 56.5 8.8 85 O 0.60CC 60060.2 56.0 8.5 86 P 0.59CC 60058.0 55.5 9.2 87 Q 0.62CC 60061.0 57.0 8.8
65/70
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TABLE 7 - continued.
BRANDS KIND OFSTEEL Ç(% in large scale) NORMALIZATION COOLING METHOD CBT (s.) ATI C(° C) HRC HARDNESS F 3 SIZE OFGRAIN 88 R 0.56CC 30057.0 54.0 8.7 89 s 0.71IC250 63.0 61.5 9.5 90 T 0.36CC 10051.0 44.0 9.6 91 U 0.50CC 10058.0 51.0 9.5 92 G 0.61IC250 62.5 56.5 9.5 93 G 0.61IC300 62.0 56.5 9.3 94 THE 0.50CC 100048.0 51.0 9.4 95 G 0.61CC 100053.5 56.5 9.5 96 G 0.61IC400 52.0 56.5 9.4 97 J 0.40CC 100042.0 46.0 9.3
* In the Table, underlined values indicate outside the range of the present invention
66/70
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TABLE 8
BRANDS STEEL TYPE REFERENCE HW (°) F1 M2C (pieces / pm ² ) YS(MPa) KISSC (ksi ^ in) TEMPERATURE(° C) TIME (min.) 71 THE 730 30 0.36 0.25 20 830 25.5 72 B 730 30 0.37 0.26 30 831 26.4 73 Ç 730 30 0.35 0.25 40 825 30.5 74 D 730 30 0.31 0.22 30 831 28.5 75 AND 730 30 0.33 0.23 40 826 29.2 76 F 730 30 0.42 0.30 40 818 29 77 G 730 30 0.30 0.23 50 835 31 78 H 730 30 0.40 0.25 10 833 26.4 79 I 730 30 0.35 0.22 40 820 26.5 80 J 730 30 0.41 0.26 50 831 27.5 81 K 730 30 0.33 0.23 20 805 29.5 82 L 730 30 0.37 0.26 40 838 26.8 83 M 730 30 0.35 0.27 10 856 27.8 84 N 730 30 0.33 0.26 30 819 28 85 O 730 30 0.30 0.23 30 823 27.7
67/70
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TABLE 8 - continued.
BRANDS STEEL TYPE REFERENCE HW (°) F1 M2C (pieces / pm ² ) YS (MPa) KISSC (ksi ^ in) TEMPERATURE(° C) TIME (min.) 86 P 730 30 0.25 0.19 20 808 29 87 Q 730 30 0.30 0.24 40 821 28.5 88 R 730 30 0.25 0.19 20 830 28.9 89 s 730 30 0.35 0.29 30 825 29 90 T 730 30 0.40 0.24 30 834 28 91 U 730 30 0.32 0.23 20 836 27.9 92 G 730 30 0.30 0.23 40 830 29.5 93 G 730 30 0.33 0.26 40 825 30.5 94 THE 620 30 0.56 0.40 0 802 24.5 95 G 630 30 0.56 0.44 0 808 23 96 G 630 30 0.52 0.41 0 795 23.7 97 J 600 30 0.65 0.41 0 780 20.8
* In the Table, underlined values indicate outside the range of the present invention.
68/70
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69/70 [00185] In the Kissc column in Table 8, the Kissc stress intensity factor (ksi ^ in) of the corresponding stretcher steel is shown.
[00186] In relation to Table 7 and Table 8, it should be seen that all chemical compositions of materials from brands 71 to 93 were within the chemical composition range of low alloy steel for tubular materials of oil fields of the invention. In addition, the F1 value was 0.38 or less, and met Expression 1 in steel materials from brands 71 to 93. In addition, the number of hexagonal M2C carbides having a grain size of 1 nm more in steel was 5 particles / pm ² or more in steel materials from brands 71 to 93. In addition, the average aspect ratio of grain boundary carbides was 3 or less in steel materials from brands 71 to 93. Therefore, the Kissc stress intensity factor (ksi ^ in) of steel materials from brands 71 to 93 was 25 ksi ^ in or more. In addition, the grain size of the anterior austenite of brands 78 and 82, in which the normalization treatment was performed, was 10 or more.
[00187] On the other hand, in brands 94, 95 and 97, the chemical composition was within the range of the invention, and Expression 2 was satisfied, but the passage time at the point Ms Tcc in the temper by the continuous cooling treatment exceeded 600 seconds. In addition, the tempering temperature was less than 680 ° C. Therefore, Rockwell hardness did not satisfy Expression 3 in the rapidly cooled material, and the F1 value exceeded 0.38 and did not satisfy Expression 1. In addition, the number of hexagonal M2C carbides having a grain size of 1 nm or more was less than 5 particles / pm ² . Therefore, the Kissc stress intensity factor (ksi ^ in) of the 94, 95 and 97 steel materials was less than 25 ksi ^ in.
[00188] And, a 96 mark, the chemical composition was within the range of the invention and Expression 2 was satisfied. However, the ATic cooling stop temperature at quenching including treatment
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70/70 isothermal was greater than 300 ° C. In addition, the tempering temperature was less than 680 ° C. Therefore, Rockwell hardness did not satisfy Expression 3 in the rapidly cooled material, and the F1 value exceeded 0.38 and did not satisfy Expression 1. In addition. the number of hexagonal M2C carbides having a grain size of 1 nm or more was less than 5 particles / pm ² . Therefore, the Kissc stress intensity factor (ksi ^ in) of the 96 brand steel material was less than 25 ksi ^ in.
[00189] Above, although the embodiment of the invention has been described, the embodiment described above is only an example of carrying out the invention. Consequently, the invention is not limited to the embodiment described above, and various modifications of the configuration described above can be made without departing from the aspect of the invention.
INDUSTRIAL APPLICABILITY [00190] According to the aspects of the invention, a low alloy steel for tubular oilfield materials can be supplied which is excellent in SSC resistance. Specifically, it is possible to supply low alloy steel for tubular oilfield materials that have a yield limit (stress test 0.2%) of grade 110 ksi or greater (758 MPa or greater) or grade 125 ksi ( 862 MPa or greater), and which is excellent in SSC resistance containing the SSC resistance in the high pressure hydrogen sulfide environment and the SSC resistance in the case where the notch is applied. Thus, industrial applicability is high.
LIST OF REFERENCE SIGNS
C10. (QUICK COOLING PROCESS FOR CONTINUOUS COOLING TREATMENT)
C11. (QUICK COOLING PROCESS INCLUDING ISOTHERMAL TREATMENT)
C12. (RELATIONSHIP BETWEEN COOLING RATE AND STEEL TUBE THICKNESS) -

权利要求:
Claims (22)
[1]
1. Tubular material from oil fields, characterized by the fact that it uses steel consisting of, as a chemical composition, in mass%,
C: more than 0.35% to 1.00%,
Si: 0.05% to 0.5%,
Mn: 0.05% to 1.0%,
Al: 0.005% to 0.10%,
Mo: more than 1.0% to 10%,
P: 0.025% or less,
S: 0.010% or less,
O: 0.01% or less,
N: 0.03% or less,
Cr: 0% to 2.0%,
V: 0% to 0.30%,
Nb: 0% to 0.1%,
Ti: 0% to 0.1%,
Zr: 0% to 0.1%,
Ca: 0% to 0.01%,
B: 0% to 0.003%, and the balance consisting of Fe and impurities, where, when the width at half height (FWHM) of the peak corresponding to the crystalline plane (211) of the so-called α phase, which is obtained by a diffraction of X-rays, is an HW in ° unit, the total width in half of the maximum HW and the carbon content expressed in% by mass in the chemical composition satisfies Expression 1 below, the expressed carbon content and molybdenum content in% by mass in the chemical composition meets Expression 2 below, a tempered martensite and a tempered bainite are included as a metallographic structure,
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[2]
2/8 a number of M2C carbides having a hexagonal crystal structure and having an equivalent circle diameter of 1 nm or more is 5 particles or more per square micron, and a yield limit of 758 MPa or more.
HW x C ^1/2 <0.38 (Expression 1)
C x Mo> 0.6 (Expression 2)
2. Oilfield tubular material according to claim 1, characterized by the fact that steel includes, as a chemical composition, in mass%
Cr: 0.1 to 2.0%.
[3]
3. Tubular material from oil fields according to claim 1 or 2, characterized by the fact that steel includes, as a chemical composition, in mass%,
V: 0.05% to 0.30%.
[4]
Tubular oilfield material according to any one of claims 1 to 3, characterized by the fact that steel includes, as a chemical composition, in mass%, at least one element between
Nb: 0.002% to 0.1%,
Ti: 0.002% to 0.1%, and
Zr: 0.002% to 0.1%
[5]
5. Tubular oilfield material according to any one of claims 1 to 4, characterized by the fact that steel includes, as a chemical composition, in mass%,
Here; 0.0003% to 0.01%
[6]
Tubular oilfield material according to any one of claims 1 to 5, characterized by the fact that steel includes, as a chemical composition, in mass%,
B: 0.0003% to 0.003%.
[7]
7. Method of producing a tubular field material
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3/8 oil as defined in any of claims 1 to 6, characterized by the fact that it consists of:
a process of hot working a piece of steel, which includes as chemical composition, in mass%,
C: more than 0.35% to 1.00%,
Si: 0.05% to 0.5%,
Mn: 0.05% to 1.0%,
Al: 0.005% to 0.10%,
Mo: more than 1.0% to 10%,
P: 0.025% or less,
S: 0.010% or less,
O: 0.01% or less,
N: 0.03% or less,
Cr: 0% to 2.0%,
V: 0% to 0.30%,
Nb: 0% to 0.1%,
Ti: 0% to 0.1%,
Zr: 0% to 0.1%,
Ca: 0% to 0.01%,
B: 0% to 0.003%, and the balance consisting of Fe and impurities and in which the carbon content and the molybdenum content expressed in mass% in the chemical composition satisfy Expression 2 below, to obtain a steel material, a tempering process of the steel material from a start tempering temperature of 850 ° C to 920 ° C after the hot working process; and a tempering process to temper the steel material after the tempering process over a temperature range of 680 ° C to the point Aci,
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4/8 where, in the tempering process, the steel material after hot work is tempered by continuous cooling under a condition in which the time taken between the temperature of the beginning of the quenching to the temperature of the beginning of transformation into martensite is 100 seconds to 600 seconds
C x Mo> 0.6 (Expression 2).
[8]
8. Method of producing a tubular oilfield material as defined in any one of claims 1 to 6, characterized by the fact that it consists of:
a process of hot working a piece of steel, which includes as chemical composition, in mass%,
C: more than 0.35% to 1.00%,
Si: 0.05% to 0.5%,
Mn: 0.05% to 1.0%,
Al: 0.005% to 0.10%,
Mo: more than 1.0% to 10%,
P: 0.025% or less,
S: 0.010% or less,
O: 0.01% or less,
N: 0.03% or less,
Cr: 0% to 2.0%,
V: 0% to 0.30%,
Nb: 0% to 0.1%,
Ti: 0% to 0.1%,
Zr: 0% to 0.1%,
Ca: 0% to 0.01%,
B: 0% to 0.003%, and the balance consisting of Fe and impurities and in which the carbon content and the molybdenum content expressed in mass% in the chemical composition satisfy Expression 2 below, to obtain a material
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5/8 steel, a process for tempering the steel material from a start tempering temperature of 850 ° C to 920 ° C, after the hot work process; and a tempering process to temper the steel material after the tempering process over a temperature range of 680 ° C to the point Aci, where, in the tempering process, as the first cooling treatment, the steel material after the The hot work process is cooled under a condition in which the cooling rate from the tempering start temperature to a temperature range that varies between an Ms point and 300 ° C without including the Ms point, is 0.7 ° C / s or more, as an isothermal treatment, the steel material after the first cooling treatment is kept under a condition in the temperature range that varies between the Ms point and 300 ° C without including the Ms point for 5 to 60 minutes, and as a second cooling treatment, the steel material after the isothermal treatment is cooled
C x Mo> 0.6 (Expression 2).
[9]
9. Production method of a tubular oilfield material according to claim 7, characterized by the fact that, in the tempering process, when the Rockwell hardness on the C scale in a central portion of the thickness of the steel material after tempering process and before the tempering process is an HRC, the steel material is hardened under a condition where Rockwell HRC hardness meets Expression 3 below
HRC> 50 x C + 26 (Expression 3).
[10]
10. Production method of a field tubular material
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6/8 oil according to claim 7 or 9, also characterized by the fact that it comprises:
a normalization process to normalize the steel material after the hot working process before the tempering process, in which, in the normalization of the material, the holding temperature is 900 ° C to 920 ° C and the holding time is from 5 minutes to 60 minutes.
[11]
11. Method of producing a tubular oilfield material according to any one of claims 7 and 9 to
10, characterized by the fact that the steel part includes, as a chemical composition, in mass%,
Cr: 0.1% to 2.0%
[12]
12. Method of producing a tubular oilfield material according to any one of claims 7 and 9 to
11, characterized by the fact that the steel part includes, as chemical composition, in mass%,
V: 0.05% to 0.30%
[13]
13. Method of producing a tubular oilfield material according to any one of claims 7 and 9 to
12, characterized by the fact that the steel part includes, as a chemical composition, in mass%, at least one element between
Nb: 0.002% to 0.1%
Ti: 0.002% to 0.1%, and
Zr: 0.002 to 0.1%
[14]
14. Method of producing a tubular oilfield material according to any one of claims 7 and 9 to
13, characterized by the fact that the steel part includes, as a chemical composition, in mass%,
Ca: 0.0003% to 0.01%.
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7/8
[15]
15. Method of producing a tubular oilfield material according to any one of claims 7 and 9 to 14, characterized by the fact that the steel part includes, as a chemical composition, in mass%,
B: 0.0003% to 0.003%
[16]
16. Production method of a tubular oilfield material according to claim 8, characterized by the fact that, in the tempering process, when the Rockwell hardness on the C scale in a central portion of the thickness of the steel material after tempering process and before the tempering process is an HRC, the steel material is cooled under a condition in which Rockwell HRC hardness meets Expression 3 below
HRC> 50 x C + 26 (Expression 3).
[17]
17. Method of producing a tubular oilfield material according to claim 8 or 16, characterized in that it additionally comprises a standardization process to normalize the steel material after the hot working process before the tempering, in which, in the normalization of the material, the holding temperature is 900 ° C to 920 ° C and the holding time is 5 minutes to 60 minutes.
[18]
18. Method of producing a tubular oilfield material according to any one of claims 8 and 16 to 17, characterized by the fact that the steel part includes, as a chemical composition, in mass%,
Cr: 0.1% to 2.0%
[19]
19. Method of producing a tubular oilfield material according to any one of claims 8 and 16 to
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8/8
18, characterized by the fact that the steel part includes, as a chemical composition, in mass%,
V: 0.05% to 0.30%
[20]
20. Method of producing a tubular oilfield material according to any one of claims 8 and 16 to
19, characterized by the fact that the steel part includes, as a chemical composition, in mass%, at least one element between
Nb: 0.002% to 0.1%
Ti: 0.002% to 0.1%, and
Zr: 0.002 to 0.1%
[21]
21. Method of producing a tubular oilfield material according to any one of claims 8 and 16 to
20, characterized by the fact that the steel part includes, as a chemical composition, in mass%,
Ca: 0.0003% to 0.01%.
[22]
22. Method of producing a tubular oilfield material according to any one of claims 8 and 16 to
21, characterized by the fact that the steel part includes, as a chemical composition, in mass%,
B: 0.0003% to 0.003%.

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同族专利:

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公开号 | 公开日

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JP5522322B1|2014-06-18|

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AU2013278437B2|2016-05-19|

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MX363648B|2019-03-28|

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JPWO2013191131A1|2016-05-26|

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EP2865775A1|2015-04-29|

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MX2014015819A|2015-03-05|

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CN104395489A|2015-03-04|

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SA113340652B1|2016-04-13|

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EA201492150A1|2015-03-31|

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AU2013278437A1|2014-11-20|

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BR112014030346A2|2017-06-27|

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AR091475A1|2015-02-04|

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US10407758B2|2019-09-10|

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EP2865775A4|2015-08-19|

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US20150114527A1|2015-04-30|

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CA2872854A1|2013-12-27|

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CA2872854C|2017-08-29|

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EP2865775B1|2018-08-08|

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IN2014DN09191A|2015-07-10|

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WO2013191131A1|2013-12-27|

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EA025937B1|2017-02-28|

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ES2690121T3|2018-11-19|

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CN104395489B|2017-04-26|

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UA115060C2|2017-09-11|

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法律状态:
2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-01-29| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2019-07-30| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2019-09-10| B25D| Requested change of name of applicant approved|Owner name: NIPPON STEEL CORPORATION (JP) |

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2020-03-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-05-05| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2012138650|2012-06-20|

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PCT/JP2013/066585|WO2013191131A1|2012-06-20|2013-06-17|Steel for oil well pipe, and method for producing same|

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