WO2018139400A1

WO2018139400A1 - Steel material, and steel material manufacturing method

Info

Publication number: WO2018139400A1
Application number: PCT/JP2018/001750
Authority: WO
Inventors: 晋士吉田; 勇次荒井; 貴志相馬; 裕紀神谷
Original assignee: 新日鐵住金株式会社
Priority date: 2017-01-24
Filing date: 2018-01-22
Publication date: 2018-08-02
Also published as: EP3575428A4; EP3575428A1; CA3049859A1; CN110234779A; JPWO2018139400A1; BR112019014676A2; US20190376167A1; MX2019008642A; JP6747524B2; RU2725389C1; AU2018213593A1

Abstract

Provided is a steel material that has a yield strength of 965MPa to 1069MPa (140ksi grade), and has superior SSC resistance. This steel material has a chemical composition that includes, by mass%, more than 0.50% and less than or equal to 0.80% C, 0.05% to 1.00% Si, 0.05% to 1.00% Mn, less than or equal to 0.025% P, less than or equal to 0.0100% S, 0.005% to 0.100% Al, 0.20% to 1.50% Cr, 0.25% to 1.50% Mo, 0.002% to 0.050% Ti, 0.0001% to 0.0050% B, 0.002% to 0.010% N, and less than or equal to 0.0100% O, the remainder consisting of Fe and unavoidable impurities. The steel material includes 0.010mass% to 0.060mass% solid solution C. Furthermore, the yield strength is 965MPa to 1069MPa, and the yield ratio is greater than or equal to 90%.

Description

Steel material and method for manufacturing steel material

The present invention relates to a steel material and a method for manufacturing the steel material, and more particularly to a steel material suitable for use in a sour environment and a method for manufacturing the steel material.

By making deep wells in oil wells and gas wells (hereinafter, oil wells and gas wells are simply referred to as “oil wells”), it is required to increase the strength of steel pipes for oil wells. Specifically, steel pipes for oil wells of 80 ksi class (yield strength is 80 to 95 ksi, that is, 551 to 655 MPa) and 95 ksi class (yield strength is 95 to 110 ksi, that is, 655 to 758 MPa) are widely used. More recently, 110 ksi class (yield strength is 110 to 125 ksi, ie, 758 to 862 MPa), 125 ksi class (yield strength is 125 ksi to 140 ksi, ie 862 to 965 MPa), and 140 ksi class (yield strength is 140 ksi to 155 ksi, ie, 965). Steel pipes for oil wells of ˜1069 MPa) are beginning to be demanded.

Many of the deep wells are sour environments containing corrosive hydrogen sulfide. Oil well steel pipes used in such a sour environment are required to have not only high strength but also resistance to sulfide stress cracking (hereinafter referred to as SSC resistance).

Techniques for improving the SSC resistance of steel materials typified by steel pipes for oil wells are disclosed in JP-A-62-253720 (Patent Document 1), JP-A-59-232220 (Patent Document 2), and JP-A-6-322478. (Patent Document 3), JP-A-8-3115551 (Patent Document 4), JP-A 2000-256783 (Patent Document 5), JP-A 2000-297344 (Patent Document 6), JP-A-2005. -350754 (Patent Document 7), JP2012-519238A (Patent Document 8) and JP2012-26030A (Patent Document 9).

Patent Document 1 proposes a method for improving the SSC resistance of oil well steel by reducing impurities such as Mn and P. Patent Document 2 proposes a method of increasing the SSC resistance of steel by performing quenching twice to refine crystal grains.

Patent Document 3 proposes a method of increasing the SSC resistance of 125 ksi-class steel materials by refining the steel structure by induction heat treatment. Patent Document 4 proposes a method of improving the SSC resistance of 110 ksi class to 140 ksi class steel pipes by increasing the hardenability of steel by using a direct quenching method and further increasing the tempering temperature.

Patent Document 5 and Patent Document 6 propose a method for improving the SSC resistance of 110 ksi-class to 140 ksi-class low alloy oil country tubular goods by controlling the form of carbides. Patent Document 7 proposes a method of increasing the SSC resistance of a steel material of 125 ksi (862 MPa) class or higher by controlling the dislocation density and the hydrogen diffusion coefficient to desired values. Patent Document 8 discloses a method for improving the SSC resistance of 125 ksi (862 MPa) grade steel by performing multiple quenching on low alloy steel containing 0.3 to 0.5% C. suggest. Patent Document 9 proposes a method of controlling the form and number of carbides by adopting a tempering process of two-stage heat treatment. More specifically, in Patent Document 9, the SSC resistance of 125 ksi (862 MPa) grade steel is improved by suppressing the number density of large M ₃ C or M ₂ C.

JP-A-62-253720 JP 59-232220 A JP-A-6-322478 JP-A-8-311551 JP 2000-256783 A JP 2000-297344 A JP 2005-350754 A Special table 2012-519238 gazette JP 2012-263030 A

However, even when the techniques disclosed in Patent Documents 1 to 9 are applied, excellent SSC resistance can be stably obtained in the case of a steel material (for example, oil well steel pipe) having a yield strength of 140 ksi class (965 to 1069 MPa). It may not be possible.

An object of the present disclosure is to provide a steel material having a yield strength of 965 to 1069 MPa (140 to 155 ksi, 140 ksi class) and excellent SSC resistance.

The steel material according to the present disclosure is, in mass%, C: more than 0.50 to 0.80%, Si: 0.05 to 1.00%, Mn: 0.05 to 1.00%, P: 0.025% Hereinafter, S: 0.0100% or less, Al: 0.005 to 0.100%, Cr: 0.20 to 1.50%, Mo: 0.25 to 1.50%, Ti: 0.002 to 0 0.050%, B: 0.0001 to 0.0050%, N: 0.002 to 0.010%, O: 0.0100% or less, V: 0 to 0.30%, Nb: 0 to 0.100 %, Ca: 0 to 0.0100%, Mg: 0 to 0.0100%, Zr: 0 to 0.0100%, Co: 0 to 0.50%, W: 0 to 0.50%, Ni: 0 It contains ˜0.50% and Cu: 0 to 0.50%, and the balance has a chemical composition composed of Fe and impurities. The steel material according to the present disclosure further contains 0.010 to 0.060 mass% of solute C. The steel material according to the present disclosure further has a yield strength of 965 to 1069 MPa and a yield ratio of 90% or more.

The method for manufacturing a steel material according to the present disclosure includes a preparation process, a quenching process, and a tempering process. In the preparation step, an intermediate steel material having the above-described chemical composition is prepared. In the quenching step, after the preparation step, the intermediate steel material at 800 to 1000 ° C. is cooled at a cooling rate of 50 ° C./min or more. In the tempering step, the quenched intermediate steel material is held at 660 ° C. to _{Ac 1} point for 10 to 90 minutes, and then cooled at an average cooling rate between 600 ° C. and 200 ° C. at 5 to 300 ° C./second.

The steel material according to the present disclosure has a yield strength of 965 to 1069 MPa (140 ksi class) and excellent SSC resistance.

FIG. 1 is a diagram showing the relationship between the amount of solute C and the fracture toughness value _K1SSC . FIG. 2A is a side view and a cross-sectional view of a DCB test piece used in the DCB test of the example. FIG. 2B is a perspective view of a wedge used in the DCB test of the example.

The inventors of the present invention have investigated and studied a method for achieving both the yield strength of 965 to 1069 MPa (140 ksi class) and the SSC resistance in steel materials expected to be used in a sour environment, and obtained the following knowledge.

Increasing the dislocation density in steel will increase the yield strength of the steel. However, dislocations can occlude hydrogen. For this reason, if the dislocation density of the steel material increases, the amount of hydrogen stored in the steel material may also increase. As a result of increasing the dislocation density, if the hydrogen concentration in the steel material increases, the SSC resistance of the steel material decreases even if high strength is obtained. Therefore, in order to achieve both high strength of 140 ksi class (965 to 1069 MPa) and SSC resistance, it seems that high strength using dislocation density is not preferable at first glance.

However, the present inventors can obtain excellent SSC resistance while increasing the yield strength to 140 ksi class (965 to 1069 MPa) using dislocation density by adjusting the amount of solute C in the steel material. I found. The reason for this is not clear, but the following reasons are possible.

There are movable dislocations and fixed dislocations in dislocations, but it is thought that solid solution C in the steel material fixes the movable dislocations to be fixed dislocations. If the movable dislocation is immobilized by the solid solution C, the disappearance of the dislocation can be suppressed, and the decrease in the dislocation density can be suppressed. In this case, the yield strength of the steel material can be maintained.

Furthermore, it is considered that the fixed dislocation formed by the solute C reduces the amount of hydrogen occluded in the steel material than the movable dislocation. Therefore, it is considered that the amount of hydrogen occluded in the steel material is reduced by increasing the density of the stationary dislocation formed by the solute C. As a result, the SSC resistance of the steel material can be improved. With this mechanism, it is considered that excellent SSC resistance can be obtained even with high strength of 140 ksi class.

As described above, the present inventors thought that the SSC resistance of the steel material can be improved while maintaining the yield strength of 140 ksi class by appropriately adjusting the amount of solute C in the steel material. Therefore, the present inventors have, in mass%, C: more than 0.50 to 0.80%, Si: 0.05 to 1.00%, Mn: 0.05 to 1.00%, P: 0.00. 025% or less, S: 0.0100% or less, Al: 0.005 to 0.100%, Cr: 0.20 to 1.50%, Mo: 0.25 to 1.50%, Ti: 0.002 To 0.050%, B: 0.0001 to 0.0050%, N: 0.002 to 0.010%, O: 0.0100% or less, V: 0 to 0.30%, Nb: 0 to 0 100%, Ca: 0 to 0.0100%, Mg: 0 to 0.0100%, Zr: 0 to 0.0100%, Co: 0 to 0.50%, W: 0 to 0.50%, Ni : 0 to 0.50% and Cu: 0 to 0.50%, the balance of the amount of solute C and yield using a steel material having a chemical composition consisting of Fe and impurities as the balance And degree was investigated the relationship between the fracture toughness value _{K 1 SSC} is an index of the SSC resistance.

[Relationship between the amount of solute C and SSC resistance]
FIG. 1 is a diagram showing the relationship between the amount of dissolved C and the fracture toughness value _K1SSC of each test number in the example. FIG. 1 was obtained by the following method. Among the examples to be described later, for steel materials in which conditions other than the solid solution C amount satisfy the range of the present embodiment, the obtained solid solution C amount (mass%) and the fracture toughness value K 1 _SSC (MPa√m) are used. FIG. 1 was created.

The yield strength YS (Yield Strength) of the steel shown in FIG. 1 was 965 to 1069 MPa (140 ksi class). The yield strength YS was adjusted by adjusting the tempering temperature. Further, regarding the SSC resistance, when the fracture toughness value K ₁ SSC, which is an index of the SSC resistance, is _30.0 MPa√m or more, it was determined that the SSC resistance was good.

Referring to FIG. 1, in a steel material satisfying the above chemical composition, if the amount of solute C is 0.010% by mass or more, the fracture toughness value K 1 _SSC is 30.0 MPa√m or more, and excellent SSC resistance is obtained. Indicated. On the other hand, in the steel material satisfying the above chemical composition, when the solid solution C amount exceeds 0.060 mass%, the fracture toughness value K 1 _SSC is less than _30.0 MPa√m. That is, it was revealed that when the amount of solute C is too high, the SSC resistance deteriorates.

This reason is not clear. However, in the range of the chemical composition and the yield strength YS of this embodiment, excellent SSC resistance can be obtained if the amount of dissolved C is 0.060% by mass or less.

As described above, by adjusting the chemical composition and tempering conditions, the yield strength YS is set to 965 to 1069 MPa (140 ksi class), and the solid solution C amount is set to 0.010 to 0.060% by mass. The toughness value K 1 _SSC is 30.0 MPa√m or more, and excellent SSC resistance can be obtained.

Therefore, in the present embodiment, the solid solution C amount of the steel material is 0.010 to 0.060 mass%.

In addition, in order to appropriately control the amount of solute C and suppress movable dislocations, the microstructure of steel is a structure mainly composed of tempered martensite and tempered bainite. The tempered martensite and the tempered bainite main body mean that the total volume ratio of the tempered martensite and the tempered bainite is 90% or more. If the microstructure of the steel is mainly tempered martensite and tempered bainite, in the steel material according to the present embodiment, the yield strength YS is 965 to 1069 MPa (140 ksi class), the yield ratio YR (the yield strength YS with respect to the tensile strength TS (Tensile Strength)). Ratio, that is, yield ratio YR (%) = yield strength YS / tensile strength TS) is 90% or more.

The steel material according to the present embodiment completed based on the above knowledge is, in mass%, C: more than 0.50 to 0.80%, Si: 0.05 to 1.00%, Mn: 0.05 to 1.%. 00%, P: 0.025% or less, S: 0.0100% or less, Al: 0.005 to 0.100%, Cr: 0.20 to 1.50%, Mo: 0.25 to 1.50 %, Ti: 0.002 to 0.050%, B: 0.0001 to 0.0050%, N: 0.002 to 0.010%, O: 0.0100% or less, V: 0 to 0.30 %, Nb: 0 to 0.100%, Ca: 0 to 0.0100%, Mg: 0 to 0.0100%, Zr: 0 to 0.0100%, Co: 0 to 0.50%, W: 0 Contains 0.5 to 0.50%, Ni: 0 to 0.50%, and Cu: 0 to 0.50%, with the balance being Fe and impurities. . The steel material according to the present embodiment further contains 0.010 to 0.060 mass% of solute C. The steel material according to the present embodiment further has a yield strength of 965 to 1069 MPa and a yield ratio of 90% or more.

In the present specification, the steel material is not particularly limited, and examples thereof include a steel pipe and a steel plate.

The chemical composition may contain one or more selected from the group consisting of V: 0.01 to 0.30% and Nb: 0.002 to 0.100%.

The chemical composition is one or two selected from the group consisting of Ca: 0.0001 to 0.0100%, Mg: 0.0001 to 0.0100%, and Zr: 0.0001 to 0.0100%. It may contain seeds or more.

The chemical composition may contain one or more selected from the group consisting of Co: 0.02 to 0.50% and W: 0.02 to 0.50%.

The chemical composition may contain one or more selected from the group consisting of Ni: 0.02 to 0.50% and Cu: 0.01 to 0.50%.

The steel material may be an oil well steel pipe.

In the present specification, the oil well steel pipe may be a line pipe steel pipe or an oil well pipe. The oil well steel pipe may be a seamless steel pipe or a welded steel pipe. An oil well pipe is, for example, a steel pipe used for casing and tubing applications.

The oil well steel pipe according to the present embodiment is preferably a seamless steel pipe. If the oil well steel pipe according to the present embodiment is a seamless steel pipe, it has a yield strength of 965 to 1069 MPa (140 ksi class) and excellent SSC resistance even if the wall thickness is 15 mm or more.

Specifically, the excellent SSC resistance refers to a solution prepared by mixing degassed 5% saline and 4 g / L Na acetate and adjusting the pH to 3.5 with hydrochloric acid, and 10% H ₂ S. In a DCB test in accordance with NACE TM0177-2005 Method D using an autoclave in which a gas and a mixed gas of 90% CO ₂ gas at a total pressure of 1 atm are enclosed, K _1SSC (MPa√m) is 30.0 MPa √m or more.

Moreover, the said solid solution C amount means the difference from C content of the chemical composition of steel materials of C amount (mass%) in the carbide | carbonized_material in steel materials. The amount of C in the carbide in the steel material is the Fe concentration <Fe> a, Cr concentration <Cr> a in the carbide (cementite and MC type carbide) obtained as a residue by performing extraction residue analysis on the steel material, Mn concentration <Mn> a, Mo concentration <Mo> a, V concentration <V> a, Nb concentration <Nb> a, and cementite specified by TEM observation of the replica film obtained by the extraction replica method Using the Fe concentration <Fe> b, Cr concentration <Cr> b, Mn concentration <Mn> b, and Mo concentration <Mo> b in the cementite obtained by performing point analysis using EDS, the formula (1 ) To formula (5).
<Mo> c = (<Fe> a + <Cr> a + <Mn> a) × <Mo> b / (<Fe> b + <Cr> b + <Mn> b) (1)
<Mo> d = <Mo> a- <Mo> c (2)
<C> a = (<Fe> a / 55.85 + <Cr> a / 52 + <Mn> a / 53.94 + <Mo> c / 95.9) / 3 × 12 (3)
<C> b = (<V> a / 50.94 + <Mo> d / 95.9 + <Nb> a / 92.9) × 12 (4)
(Solution C amount) = <C> − (<C> a + <C> b) (5)
In addition, in this specification, cementite means the carbide | carbonized_material whose Fe content is 50 mass% or more.

The method for manufacturing a steel material according to the present embodiment includes a preparation process, a quenching process, and a tempering process. In the preparation step, an intermediate steel material having the above-described chemical composition is prepared. In the quenching step, the intermediate steel material at 800 to 1000 ° C. is cooled at a cooling rate of 50 ° C./min or more after the preparation step. In the tempering step, the quenched intermediate steel material is held at 660 ° C. to _{Ac 1} point for 10 to 90 minutes, and then cooled at an average cooling rate between 600 ° C. and 200 ° C. at 5 to 300 ° C./second.

In this specification, the intermediate steel material corresponds to a raw pipe when the final product is a steel pipe, and corresponds to a plate-shaped steel material when the final product is a steel plate.

The preparation process of the manufacturing method may include a material preparation process for preparing a material having the above-described chemical composition and a hot working process for manufacturing an intermediate steel material by hot working the material.

Hereinafter, the steel material according to the present embodiment will be described in detail. “%” Regarding an element means mass% unless otherwise specified.

[Chemical composition]
The chemical composition of the steel material according to the present embodiment contains the following elements.

C: Over 0.50 to 0.80%
Carbon (C) increases the hardenability and increases the strength of the steel material. C further promotes the spheroidization of carbides during tempering during the manufacturing process, and increases the SSC resistance of the steel material. If the carbide is dispersed, the strength of the steel material is further increased. If the C content is too low, these effects cannot be obtained. On the other hand, if the C content is too high, the toughness of the steel material is lowered and fire cracks are likely to occur. Therefore, the C content is more than 0.50 to 0.80%. The minimum with preferable C content is 0.51%. The upper limit with preferable C content is 0.70%, More preferably, it is 0.62%.

Si: 0.05 to 1.00%
Silicon (Si) deoxidizes steel. If the Si content is too low, this effect cannot be obtained. On the other hand, if the Si content is too high, the SSC resistance of the steel material decreases. Therefore, the Si content is 0.05 to 1.00%. The minimum of preferable Si content is 0.15%, More preferably, it is 0.20%. The upper limit of the preferable Si content is 0.85%, more preferably 0.50%.

Mn: 0.05 to 1.00%
Manganese (Mn) deoxidizes steel. Mn further enhances hardenability. If the Mn content is too low, these effects cannot be obtained. On the other hand, if the Mn content is too high, Mn segregates at grain boundaries together with impurities such as P and S. In this case, the SSC resistance of the steel material decreases. Therefore, the Mn content is 0.05 to 1.00%. The minimum of preferable Mn content is 0.25%, More preferably, it is 0.30%. The upper limit of the preferable Mn content is 0.90%, more preferably 0.80%.

P: 0.025% or less Phosphorus (P) is an impurity. That is, the P content is more than 0%. P segregates at the grain boundaries and decreases the SSC resistance of the steel material. Therefore, the P content is 0.025% or less. The upper limit with preferable P content is 0.020%, More preferably, it is 0.015%. The P content is preferably as low as possible. However, the extreme reduction of the P content significantly increases the manufacturing cost. Therefore, when industrial production is considered, the minimum with preferable P content is 0.0001%, More preferably, it is 0.0003%, More preferably, it is 0.001%.

S: 0.0100% or less Sulfur (S) is an impurity. That is, the S content is more than 0%. S segregates at the grain boundaries and decreases the SSC resistance of the steel material. Therefore, the S content is 0.0100% or less. The upper limit with preferable S content is 0.0050%, More preferably, it is 0.0030%. The S content is preferably as low as possible. However, the extreme reduction of the S content greatly increases the manufacturing cost. Therefore, when industrial production is considered, the minimum with preferable S content is 0.0001%, More preferably, it is 0.0002%, More preferably, it is 0.0003%.

Al: 0.005 to 0.100%
Aluminum (Al) deoxidizes steel. If the Al content is too low, this effect cannot be obtained, and the SSC resistance of the steel material decreases. On the other hand, if the Al content is too high, coarse oxide inclusions are generated and the SSC resistance of the steel material is lowered. Therefore, the Al content is 0.005 to 0.100%. The minimum with preferable Al content is 0.015%, More preferably, it is 0.020%. The upper limit with preferable Al content is 0.080%, More preferably, it is 0.060%. As used herein, “Al” content means “acid-soluble Al”, that is, the content of “sol. Al”.

Cr: 0.20 to 1.50%
Chromium (Cr) improves the hardenability of the steel material. Further, Cr increases the temper softening resistance of the steel material and enables high temperature tempering. As a result, the SSC resistance of the steel material is increased. If the Cr content is too low, the above effect cannot be obtained. On the other hand, if the Cr content is too high, the toughness and SSC resistance of the steel material will decrease. Therefore, the Cr content is 0.20 to 1.50%. The minimum with preferable Cr content is 0.25%, More preferably, it is 0.30%. The upper limit with preferable Cr content is 1.30%.

Mo: 0.25 to 1.50%
Molybdenum (Mo) improves the hardenability of the steel material. Mo further generates fine carbides and increases the temper softening resistance of the steel material. As a result, Mo increases the SSC resistance of the steel material by high temperature tempering. If the Mo content is too low, this effect cannot be obtained. On the other hand, if the Mo content is too high, the above effect is saturated. Therefore, the Mo content is 0.25 to 1.50%. The minimum with preferable Mo content is 0.50%, More preferably, it is 0.65%. The upper limit with preferable Mo content is 1.20%, More preferably, it is 1.00%.

Ti: 0.002 to 0.050%
Titanium (Ti) forms a nitride and refines crystal grains by a pinning effect. Thereby, the intensity | strength of steel materials increases. If the Ti content is too low, this effect cannot be obtained. On the other hand, if the Ti content is too high, the Ti nitride becomes coarse and the SSC resistance of the steel material decreases. Therefore, the Ti content is 0.002 to 0.050%. The minimum with preferable Ti content is 0.003%, More preferably, it is 0.005%. The upper limit with preferable Ti content is 0.030%, More preferably, it is 0.020%.

B: 0.0001 to 0.0050%
Boron (B) is dissolved in steel to increase the hardenability of the steel material and increase the strength of the steel material. If the B content is too low, this effect cannot be obtained. On the other hand, if the B content is too high, coarse nitrides are generated and the SSC resistance of the steel material is lowered. Therefore, the B content is 0.0001 to 0.0050%. The minimum with preferable B content is 0.0003%, More preferably, it is 0.0007%. The upper limit with preferable B content is 0.0035%, More preferably, it is 0.0025%.

N: 0.002 to 0.010%
Nitrogen (N) is inevitably contained. N combines with Ti to form fine nitrides and refines the crystal grains. On the other hand, if the N content is too high, N forms coarse nitrides and the SSC resistance of the steel material decreases. Therefore, the N content is 0.002 to 0.010%. The upper limit with preferable N content is 0.005%, More preferably, it is 0.004%.

O: 0.0100% or less Oxygen (O) is an impurity. That is, the O content is over 0%. O forms a coarse oxide and reduces the corrosion resistance of the steel material. Therefore, the O content is 0.0100% or less. The upper limit with preferable O content is 0.0030%, More preferably, it is 0.0020%. The O content is preferably as low as possible. However, the extreme reduction of the O content greatly increases the manufacturing cost. Therefore, when considering industrial production, the preferable lower limit of the O content is 0.0001%, more preferably 0.0002%, and still more preferably 0.0003%.

The balance of the chemical composition of the steel material according to the present embodiment is composed of Fe and impurities. Here, the impurities are mixed from ore as a raw material, scrap, or production environment when industrially producing steel materials, and are allowed within a range that does not adversely affect the steel materials according to the present embodiment. Means what will be done.

[Arbitrary elements]
The chemical composition of the steel material described above may further include one or more selected from the group consisting of V and Nb in place of part of Fe. Any of these elements is an arbitrary element and improves the SSC resistance of the steel material.

V: 0 to 0.30%
Vanadium (V) is an optional element and may not be contained. That is, the V content may be 0%. When contained, V combines with C or N to form carbide, nitride, carbonitride, etc. (hereinafter referred to as “carbonitride etc.”). These carbonitrides and the like refine the steel substructure by the pinning effect and increase the SSC resistance of the steel material. V further forms fine carbides during tempering. Fine carbide increases the temper softening resistance of the steel material and increases the strength of the steel material. Further, since V becomes a spherical MC type carbide, the formation of acicular M ₂ C type carbide is suppressed, and the SSC resistance of the steel material is improved. If V is contained even a little, the above effect can be obtained to some extent. However, if the V content is too high, the toughness of the steel material decreases. Therefore, the V content is 0 to 0.30%. The minimum with preferable V content is more than 0%, More preferably, it is 0.01%, More preferably, it is 0.02%. The upper limit with preferable V content is 0.20%, More preferably, it is 0.15%, More preferably, it is 0.12%.

Nb: 0 to 0.100%
Niobium (Nb) is an optional element and may not be contained. That is, the Nb content may be 0%. When contained, Nb forms carbonitride and the like. These carbonitrides refine the substructure of the steel material by the pinning effect, and improve the SSC resistance of the steel material. Further, since Nb becomes a spherical MC type carbide, the formation of acicular M ₂ C type carbide is suppressed, and the SSC resistance of the steel material is improved. If Nb is contained even a little, the above effect can be obtained to some extent. However, if the Nb content is too high, carbonitrides and the like are excessively generated, and the SSC resistance of the steel material is lowered. Therefore, the Nb content is 0 to 0.100%. The minimum with preferable Nb content is more than 0%, More preferably, it is 0.002%, More preferably, it is 0.003%, More preferably, it is 0.007%. The upper limit with preferable Nb content is 0.025%, More preferably, it is 0.020%.

The total content of V and Nb is preferably 0.30% or less, and more preferably 0.20% or less.

The chemical composition of the steel material described above may further include one or more selected from the group consisting of Ca, Mg, and Zr instead of part of Fe. Any of these elements is an arbitrary element and improves the SSC resistance of the steel material.

Ca: 0 to 0.0100%
Calcium (Ca) is an optional element and may not be contained. That is, the Ca content may be 0%. When contained, Ca refines sulfides in the steel material and improves the SSC resistance of the steel material. If Ca is contained even a little, the above effect can be obtained to some extent. However, if the Ca content is too high, the oxide in the steel material becomes coarse, and the SSC resistance of the steel material decreases. Therefore, the Ca content is 0 to 0.0100%. The minimum with preferable Ca content is more than 0%, More preferably, it is 0.0001%, More preferably, it is 0.0003%, More preferably, it is 0.0006%. The upper limit with preferable Ca content is 0.0025%, More preferably, it is 0.0020%.

Mg: 0 to 0.0100%
Magnesium (Mg) is an optional element and may not be contained. That is, the Mg content may be 0%. When contained, Mg renders S in the steel material harmless as a sulfide and improves the SSC resistance of the steel material. If Mg is contained even a little, the above effect can be obtained to some extent. However, if the Mg content is too high, the oxide in the steel material becomes coarse, and the SSC resistance of the steel material decreases. Therefore, the Mg content is 0 to 0.0100%. The lower limit of the Mg content is preferably more than 0%, more preferably 0.0001%, still more preferably 0.0003%, still more preferably 0.0006%, and still more preferably 0.0010%. It is. The upper limit with preferable Mg content is 0.0025%, More preferably, it is 0.0020%.

Zr: 0 to 0.0100%
Zirconium (Zr) is an optional element and may not be contained. That is, the Zr content may be 0%. When contained, Zr refines sulfides in the steel material and improves the SSC resistance of the steel material. If Zr is contained even a little, the above effect can be obtained to some extent. However, if the Zr content is too high, the oxide in the steel material becomes coarse. Therefore, the Zr content is 0 to 0.0100%. The minimum with preferable Zr content is more than 0%, More preferably, it is 0.0001%, More preferably, it is 0.0003%, More preferably, it is 0.0006%. The upper limit with preferable Zr content is 0.0025%, More preferably, it is 0.0020%.

The total content when containing two or more selected from the group consisting of Ca, Mg and Zr is preferably 0.0100% or less, and 0.0050% or less. Is more preferable.

The chemical composition of the steel material described above may further include one or more selected from the group consisting of Co and W instead of part of Fe. All of these elements are optional elements, and form a protective corrosion film in a hydrogen sulfide environment and suppress hydrogen intrusion. Thereby, these elements increase the SSC resistance of the steel material.

Co: 0 to 0.50%
Cobalt (Co) is an optional element and may not be contained. That is, the Co content may be 0%. When contained, Co forms a protective corrosion film in a hydrogen sulfide environment and suppresses hydrogen intrusion. Thereby, SSC resistance of steel materials is improved. If Co is contained even a little, the above effect can be obtained to some extent. However, if the Co content is too high, the hardenability of the steel material decreases and the strength of the steel material decreases. Therefore, the Co content is 0 to 0.50%. The minimum with preferable Co content is more than 0%, More preferably, it is 0.02%, More preferably, it is 0.05%. The upper limit with preferable Co content is 0.45%, More preferably, it is 0.40%.

W: 0 to 0.50%
Tungsten (W) is an optional element and may not be contained. That is, the W content may be 0%. When contained, W forms a protective corrosion film in a hydrogen sulfide environment and suppresses hydrogen intrusion. Thereby, SSC resistance of steel materials is improved. If W is contained even a little, the above effect can be obtained to some extent. However, if the W content is too high, coarse carbides are generated in the steel material, and the SSC resistance of the steel material decreases. Therefore, the W content is 0 to 0.50%. The minimum with preferable W content is more than 0%, More preferably, it is 0.02%, More preferably, it is 0.05%. The upper limit with preferable W content is 0.45%, More preferably, it is 0.40%.

The chemical composition of the steel material described above may further include one or more selected from the group consisting of Ni and Cu instead of a part of Fe. All of these elements are optional elements and enhance the hardenability of the steel.

Ni: 0 to 0.50%
Nickel (Ni) is an optional element and may not be contained. That is, the Ni content may be 0%. When contained, Ni increases the hardenability of the steel material and increases the strength of the steel material. If Ni is contained even a little, the above effect can be obtained to some extent. However, if the Ni content is too high, local corrosion is promoted and the SSC resistance of the steel material is lowered. Therefore, the Ni content is 0 to 0.50%. The minimum with preferable Ni content is more than 0%, More preferably, it is 0.02%, More preferably, it is 0.05%. The upper limit with preferable Ni content is 0.35%, More preferably, it is 0.25%.

Cu: 0 to 0.50%
Copper (Cu) is an optional element and may not be contained. That is, the Cu content may be 0%. When contained, Cu increases the hardenability of the steel material and increases the strength of the steel material. If Cu is contained even a little, the above effect can be obtained to some extent. However, if the Cu content is too high, the hardenability of the steel material becomes too high, and the SSC resistance of the steel material decreases. Therefore, the Cu content is 0 to 0.50%. The minimum with preferable Cu content is more than 0%, More preferably, it is 0.01%, More preferably, it is 0.02%, More preferably, it is 0.05%. The upper limit with preferable Cu content is 0.35%, More preferably, it is 0.25%.

[Solution C amount]
The steel material according to the present embodiment contains 0.010 to 0.060 mass% of solute C. If the amount of solute C is less than 0.010% by mass, dislocations in the steel material are not sufficiently fixed, and excellent SSC resistance of the steel material cannot be obtained. On the other hand, if the amount of solute C exceeds 0.060% by mass, the SSC resistance of the steel material is lowered. Therefore, the amount of solid solution C is 0.010 to 0.060% by mass. The minimum with the preferable amount of solute C is 0.020 mass%, More preferably, it is 0.030 mass%.

The amount of solute C in this range can be obtained, for example, by controlling the tempering holding time and the cooling rate of the tempering process. The reason for this is as follows.

The amount of dissolved C is the highest immediately after quenching. Immediately after quenching, C is in solid solution except for a small amount precipitated as a carbide during quenching. Thereafter, in the tempering step, C is partially precipitated as carbides by soaking. As a result, the amount of solute C decreases toward the thermal equilibrium concentration at the tempering temperature. When the holding time for tempering is too short, this effect cannot be obtained and the amount of dissolved C becomes too high. On the other hand, when the holding time of tempering is too long, the amount of solute C approaches the thermal equilibrium concentration and hardly changes. Therefore, in this embodiment, the tempering holding time is 10 to 90 minutes.

In cooling after tempering, when the cooling rate is slow, the solid solution C re-deposits during the temperature drop. In the conventional method for producing a steel material, the cooling after tempering is performed by cooling, so that the cooling rate is slow. Therefore, the amount of solute C was almost 0% by mass. Therefore, in the present embodiment, the cooling rate after tempering is increased to obtain a solid solution C amount of 0.010 to 0.060 mass%.

As a cooling method, for example, the steel material is continuously forcedly cooled from the tempering temperature, and the surface temperature of the steel material is continuously reduced. As such a continuous cooling treatment, for example, there are a method of immersing a steel material in a water tank and cooling, and a method of accelerating cooling of the steel material by shower water cooling, mist cooling or forced air cooling.

The cooling rate after tempering is measured at the site that is cooled most slowly in the cross section of the tempered steel material (for example, the central part of the steel material thickness when both surfaces are forcibly cooled). Specifically, when the steel material is a steel plate, a cooling rate after tempering can be measured by inserting a sheath-type thermocouple in the center of the plate thickness of the steel plate and measuring the temperature. When the steel material is a steel pipe, a cooling rate after tempering can be measured by inserting a sheath-type thermocouple in the center of the thickness of the steel pipe and measuring the temperature. Moreover, when forcedly cooling only the one side surface of steel materials, the surface temperature of the non-forced cooling side of steel materials can be measured with a non-contact type infrared thermometer.

The temperature range between 600 ° C and 200 ° C is a relatively fast temperature range for C diffusion. Therefore, in this embodiment, the average cooling rate between 600 ° C. and 200 ° C. is set to 5 ° C./second or more.

On the other hand, if the cooling rate after tempering is too fast, C that has been dissolved after the tempering soaking is hardly precipitated. As a result, the amount of solute C may be excessive. In this case, the SSC resistance of the steel material decreases. Therefore, in this embodiment, the cooling rate after tempering is set to 300 ° C./second or less.

In this case, the amount of dissolved C can be 0.010 to 0.060% by mass. However, the amount of solute C in the steel material may be adjusted to 0.010 to 0.060 mass% by other methods.

[Calculation method of solid solution C amount]
Solid solution C amount means the difference from C content of the chemical composition of steel materials of C amount (mass%) in the carbide | carbonized_material in steel materials. The amount of C in the carbide in the steel material is the Fe concentration <Fe> a, Cr concentration <Cr> a in the carbide (cementite and MC type carbide) obtained as a residue by performing extraction residue analysis on the steel material, Mn concentration <Mn> a, Mo concentration <Mo> a, V concentration <V> a, Nb concentration <Nb> a, and cementite specified by TEM observation of the replica film obtained by the extraction replica method Using the Fe concentration <Fe> b, Cr concentration <Cr> b, Mn concentration <Mn> b, and Mo concentration <Mo> b in the cementite obtained by performing point analysis using EDS, the formula (1 ) To formula (5).
<Mo> c = (<Fe> a + <Cr> a + <Mn> a) × <Mo> b / (<Fe> b + <Cr> b + <Mn> b) (1)
<Mo> d = <Mo> a- <Mo> c (2)
<C> a = (<Fe> a / 55.85 + <Cr> a / 52 + <Mn> a / 53.94 + <Mo> c / 95.9) / 3 × 12 (3)
<C> b = (<V> a / 50.94 + <Mo> d / 95.9 + <Nb> a / 92.9) × 12 (4)
(Solution C amount) = <C> − (<C> a + <C> b) (5)
In addition, in this specification, cementite means the carbide | carbonized_material whose Fe content is 50 mass% or more. Hereinafter, the calculation method of the solid solution C amount will be described in detail.

[Quantification of C content of steel]
When the steel material is a plate material, a chip-like analysis sample is collected from the plate thickness center portion, and when the steel material is a tube material, the chip-shaped analysis sample is collected from the thickness center portion. The C content (mass%) is analyzed by combustion in an oxygen stream-infrared absorption method. This is the C content (<C>) of the steel material.

[Calculation of C amount precipitated as carbide (precipitation C amount)]
The amount of precipitated C is calculated by the following procedure 1 to procedure 4. Specifically, extraction residue analysis is performed in Procedure 1. By the extraction replica method using a transmission electron microscope (hereinafter referred to as “TEM”) and the energy dispersive X-ray spectroscopy (hereinafter referred to as “EDS”) in Step 2. Conduct element concentration analysis in cementite (hereinafter referred to as “EDS analysis”). In step 3, the Mo content is adjusted. In step 4, the amount of precipitated C is calculated.

[Procedure 1. Determination of Fe, Cr, Mn, Mo, V and Nb residue amounts by extraction residue analysis]
In the procedure 1, the carbides in the steel material are captured as a residue, and the Fe, Cr, Mn, Mo, V, and Nb contents in the residue are determined. Here, “carbide” is a general term for cementite (M3C type carbide) and MC type carbide. The specific procedure is as follows. When the steel material is a plate material, a columnar test piece having a diameter of 6 mm and a length of 50 mm is collected from the central portion of the plate thickness. When the steel material is a steel pipe, a cylindrical test piece having a diameter of 6 mm and a length of 50 mm is collected from the center of the thickness of the steel pipe so that the thickness center is the center of the cross section. The collected specimen surface is polished by about 50 μm by preliminary electrolytic polishing to obtain a new surface. The electropolished test piece is electrolyzed with an electrolytic solution 10% acetylacetone + 1% tetraammonium + methanol. Residues are captured by passing the electrolytic solution after electrolysis through a 0.2 μm filter. The obtained residue is acid-decomposed, and the concentrations of Fe, Cr, Mn, Mo, V, and Nb are quantified in units of mass% by ICP (inductively coupled plasma) emission analysis. These concentrations are defined as <Fe> a, <Cr> a, <Mn> a, <Mo> a, <V> a, and <Nb> a, respectively.

[Procedure 2. Determination of Fe, Cr, Mn, and Mo contents in cementite by extraction replica method and EDS]
In procedure 2, the contents of Fe, Cr, Mn, and Mo in cementite are determined. The specific procedure is as follows. When the steel material is a plate material, a micro test piece is cut out from the central portion of the plate thickness, and when the steel material is a steel pipe, the micro test piece is cut out and finished by mirror polishing. The test piece is immersed in a 3% nital etchant for 10 minutes to corrode the surface. The surface is covered with a carbon vapor deposition film. A test piece whose surface is covered with a vapor deposition film is immersed in a 5% nital corrosive solution, held for 20 minutes, and the vapor deposition film is peeled off. The peeled deposited film is washed with ethanol, then scooped with a sheet mesh and dried. This deposited film (replica film) is observed with a TEM, and 20 cementites are subjected to point analysis by EDS. The Fe, Cr, Mn, and Mo concentrations when the total of alloy elements excluding carbon in cementite is 100% are quantified in units of mass%. The concentration of 20 cementites is quantified, and the arithmetic average value of each element is defined as <Fe> b, <Cr> b, <Mn> b, <Mo> b.

[Procedure 3. Adjustment of Mo amount]
Subsequently, the Mo concentration in the carbide is determined. Here, Fe, Cr, Mn, and Mo are concentrated to cementite. On the other hand, V, Nb, and Mo are concentrated in MC type carbides. That is, Mo is concentrated to both cementite and MC type carbide by tempering. Therefore, about Mo amount, it calculates separately about cementite and MC type carbide. A part of V may also concentrate in cementite. However, the amount of V enriched in cementite is negligibly small compared to the amount of enriched MC type carbide. Therefore, in obtaining the amount of dissolved C, V is considered to be concentrated only in MC type carbides.

Specifically, the amount of Mo precipitated as cementite (<Mo> c) is calculated by the equation (1).
<Mo> c = (<Fe> a + <Cr> a + <Mn> a) × <Mo> b / (<Fe> b + <Cr> b + <Mn> b) (1)

On the other hand, the amount of Mo precipitated as MC type carbide (<Mo> d) is calculated in units of mass% according to the formula (2).
<Mo> d = <Mo> a- <Mo> c (2)

[Procedure 4. Calculation of amount of precipitated C]
The amount of precipitated C is calculated as the sum of the amount of C precipitated as cementite (<C> a) and the amount of C precipitated as MC type carbide (<C> b). <C> a and <C> b are calculated in units of mass% according to formula (3) and formula (4), respectively. In addition, Formula (3) is a formula derived from the structure of cementite being M ₃ C type (M includes Fe, Cr, Mn, and Mo).
<C> a = (<Fe> a / 55.85 + <Cr> a / 52 + <Mn> a / 53.94 + <Mo> c / 95.9) / 3 × 12 (3)
<C> b = (<V> a / 50.94 + <Mo> d / 95.9 + <Nb> a / 92.9) × 12 (4)

From the above, the amount of precipitated C is <C> a + <C> b.

[Calculation of solute C content]
The amount of solid solution C (hereinafter also referred to as <C> c) is calculated as a difference between the C content (<C>) of the steel material and the amount of precipitated C in units of mass% using Equation (5).
<C> c = <C> − (<C> a + <C> b) (5)

[Microstructure]
The microstructure of the steel material according to the present embodiment is mainly composed of tempered martensite and tempered bainite. More specifically, the microstructure is composed of tempered martensite and / or tempered bainite having a volume ratio of 90% or more. That is, in the microstructure, the total volume ratio of tempered martensite and tempered bainite is 90% or more. The balance of the microstructure is, for example, retained austenite. If the microstructure of the steel material having the above chemical composition contains 90% or more of the total volume ratio of tempered martensite and tempered bainite, the yield strength is 965 to 1069 MPa (140 ksi class), and the yield ratio is 90%. That's it.

In this embodiment, if the yield strength YS is 965 to 1069 MPa (140 ksi class) and YR is 90% or more, the microstructure is a sum of the volume ratios of tempered martensite and tempered bainite being 90% or more. And Preferably, the microstructure consists only of tempered martensite and / or tempered bainite.

In addition, when calculating | requiring the sum total of the volume ratio of tempered martensite and tempered bainite by observation, it can obtain | require with the following method. When the steel material is a plate material, a small piece having an observation surface with a rolling direction of 10 mm and a plate width direction of 10 mm is cut out from the center portion of the plate thickness. When the steel material is a steel pipe, a small piece having an observation surface of 10 mm in the pipe axis direction and 10 mm in the pipe circumferential direction is cut out from the central portion of the wall thickness. After the observation surface is polished to a mirror surface, it is immersed in a nital etchant for about 10 seconds to reveal the structure by etching. The etched observation surface is observed with a scanning electron microscope (SEM: Scanning Electron Microscope) for 10 fields of view with a secondary electron image. The visual field area is 400 μm ² (5000 × magnification). In each field of view, tempered martensite and tempered bainite are identified from the contrast. The total area fraction of the specified tempered martensite and tempered bainite is determined. In the present embodiment, the arithmetic average value of the total area fractions of tempered martensite and tempered bainite obtained from all the visual fields is defined as the volume ratio of tempered martensite and tempered bainite.

[Shape of steel]
The shape of the steel material by this embodiment is not specifically limited. The steel material is, for example, a steel pipe or a steel plate. When the steel material is an oil well steel pipe, the steel material is preferably a seamless steel pipe. In this case, the preferred thickness is 9 to 60 mm. The steel material according to the present embodiment is particularly suitable for use as a thick oil well steel pipe. More specifically, even if the steel material according to the present embodiment is a steel pipe for oil well with a thickness of 15 mm or more, and further 20 mm or more, excellent strength and SSC resistance are exhibited.

[Yield strength YS and yield ratio YR of steel]
The yield strength YS of the steel material according to this embodiment is 965 to 1069 MPa (140 ksi class), and the yield ratio YR is 90% or more. The yield strength YS as used in this specification means the stress at the time of 0.65% elongation obtained by the tensile test. In short, the strength of the steel material according to the present embodiment is 140 ksi class. The steel material according to the present embodiment has excellent SSC resistance by satisfying the above-described chemical composition, solute C amount, and microstructure even with such high strength.

[SSC resistance of steel]
The SSC resistance of the steel material according to the present embodiment can be evaluated by a DCB test based on NACE TM0177-2005 Method D. The solution is mixed with degassed 5% saline and 4 g / L Na acetate and adjusted to pH 3.5 with hydrochloric acid. The gas sealed in the autoclave is a mixed gas of 10% H ₂ S gas and 90% CO ₂ gas with a total pressure of 1 atm. Thereafter, the DCB test piece into which the wedges are driven is sealed in a container, and kept at 24 ° C. for 3 weeks while stirring the solution and continuously blowing the mixed gas. The K 1 _SSC (MPa√m) of the steel material according to the present embodiment obtained under the above conditions is 30.0 MPa√m or more.

[Production method]
The method for manufacturing a steel material according to the present embodiment includes a preparation process, a quenching process, and a tempering process. The preparation process may include a material preparation process and a hot working process. This embodiment demonstrates the manufacturing method of the steel pipe for oil wells as an example of the manufacturing method of steel materials. The manufacturing method of an oil well steel pipe includes a step of preparing a raw pipe (preparation step) and a step of quenching and tempering the raw pipe to obtain a steel pipe for oil well (quenching step and tempering step). Hereinafter, each process is explained in full detail.

[Preparation process]
In the preparation step, an intermediate steel material having the above-described chemical composition is prepared. If intermediate steel has the said chemical composition, a manufacturing method will not be specifically limited. The intermediate steel material here is a plate-shaped steel material when the final product is a steel plate, and is a raw tube when the final product is a steel pipe.

Preferably, the preparation step may include a step of preparing a raw material (raw material preparation step) and a step of hot working the raw material to produce an intermediate steel material (hot working step). Hereinafter, the case where a raw material preparation process and a hot processing process are included is explained in full detail.

[Material preparation process]
In the material preparation step, the material is manufactured using molten steel having the above-described chemical composition. Specifically, a slab (slab, bloom, or billet) is manufactured by continuous casting using molten steel. You may manufacture an ingot by the ingot-making method using molten steel. If necessary, the billet may be produced by rolling the slab, bloom or ingot into pieces. The material (slab, bloom, or billet) is manufactured by the above process.

[Hot working process]
In the hot working process, the prepared material is hot worked to produce an intermediate steel material. When the steel material is a steel pipe, the intermediate steel material corresponds to a raw pipe. First, the billet is heated in a heating furnace. The heating temperature is not particularly limited, but is, for example, 1100 to 1300 ° C. The billet extracted from the heating furnace is hot-worked to produce a raw pipe (seamless steel pipe). For example, the Mannesmann method is performed as hot working to manufacture a raw tube. In this case, the round billet is pierced and rolled by a piercing machine. In the case of piercing and rolling, the piercing ratio is not particularly limited, but is, for example, 1.0 to 4.0. The round billet that has been pierced and rolled is further hot-rolled by a mandrel mill, a reducer, a sizing mill, or the like into a blank tube. The cumulative reduction in area in the hot working process is, for example, 20 to 70%.

The blank tube may be manufactured from the billet by other hot working methods. For example, in the case of a short thick-walled steel material such as a coupling, the raw pipe may be manufactured by forging such as the Erhard method. An element pipe is manufactured by the above process. The thickness of the raw tube is not particularly limited, but is 9 to 60 mm, for example.

The raw tube manufactured by hot working may be air-cooled (As-Rolled). Steel pipes manufactured by hot working may be directly quenched after hot pipe making without cooling to room temperature, or may be quenched after supplementary heating (reheating) after hot pipe making. . However, when quenching directly after quenching or after supplementary heating, it is preferable to stop cooling during quenching or to perform slow cooling for the purpose of suppressing quench cracking.

In the case of direct quenching after hot pipe making or after hardening after hot pipe making, the purpose of removing residual stress is to perform stress relief annealing after quenching and before the next heat treatment. (SR processing) may be performed.

As described above, intermediate steel materials are prepared in the preparation process. The intermediate steel material may be manufactured by the above-described preferable process, or an intermediate steel material manufactured by a third party, or a factory other than the factory where the quenching process and the tempering process described below are performed, and other establishments. You may prepare the intermediate steel materials manufactured by. Hereinafter, the quenching process will be described in detail.

[Quenching process]
In the quenching step, quenching is performed on the prepared intermediate steel material (element tube). In the present specification, “quenching” means quenching an intermediate steel material of A ₃ points or more. A preferable quenching temperature is 800 to 1000 ° C. The quenching temperature corresponds to the surface temperature of the intermediate steel material measured by a thermometer installed on the outlet side of the apparatus that performs the final hot working when directly quenching is performed after the hot working. The quenching temperature further corresponds to the temperature of the furnace that performs the supplemental heating when the supplemental heating is performed after the hot working and then the quenching is performed.

As the quenching method, for example, the raw tube is continuously cooled from the quenching start temperature, and the surface temperature of the raw tube is continuously reduced. The method for the continuous cooling treatment is not particularly limited. Examples of the continuous cooling treatment method include a method in which the raw tube is immersed and cooled in a water tank, and a method in which the raw tube is accelerated and cooled by shower water cooling or mist cooling.

If the cooling rate at the time of quenching is too slow, the microstructure is mainly composed of martensite and bainite, and the mechanical performance defined in this embodiment cannot be obtained. Therefore, as described above, in the method for manufacturing a steel material according to the present embodiment, the intermediate steel material is rapidly cooled during quenching. Specifically, in the quenching step, an average cooling rate in the range where the surface temperature of the intermediate steel material (element tube) during quenching is in the range of 800 to 500 ° C. is defined as a quenching cooling rate CR _800-500 . The quenching cooling rate CR _800-500 is 50 ° C./min or more. The lower limit of the preferred quenching cooling rate CR _800-500 is 100 ° C./min, more preferably 250 ° C./min. The upper limit of the quenching cooling rate CR _800-500 is not particularly limited, but is, for example, 60000 ° C./min.

Preferably, the element tube is heated in the austenite region a plurality of times and then quenched. In this case, since the austenite grains before quenching are refined, the SSC resistance of the steel material is increased. By performing the quenching treatment a plurality of times, heating in the austenite region may be repeated a plurality of times, or by performing a normalization treatment and a quenching treatment, the heating in the austenite region may be repeated a plurality of times. Hereinafter, the tempering step will be described in detail.

[Tempering process]
A tempering process is implemented after implementing the above-mentioned hardening process. The tempering temperature is appropriately adjusted according to the chemical composition of the steel material and the yield strength YS to be obtained. In other words, the tempering temperature is adjusted for the base tube having the chemical composition of the present embodiment, and the yield strength YS of the steel material is adjusted to 965 to 1069 MPa (140 ksi class), and the YR of the steel material is adjusted to 90% or more.

A preferable tempering temperature is 660 ° C. to _{Ac 1} point. When the tempering temperature is 660 ° C. or higher, the carbide is sufficiently spheroidized and the SSC resistance is further improved.

If the holding time of tempering (tempering time) is too short, the precipitation of carbides does not proceed, and the amount of solute C becomes excessive. Even if the tempering time is too long, the amount of dissolved C hardly changes. Therefore, the tempering time is set to 10 to 90 minutes in order to control the solid solution C amount within an appropriate range. A preferred lower limit of the tempering time is 15 minutes. The upper limit with preferable tempering time is 70 minutes, More preferably, it is 60 minutes. In addition, when steel materials are steel pipes, compared with other shapes, the temperature dispersion | variation of a steel pipe tends to generate | occur | produce during the soaking | uniform-heating maintenance of temper. Therefore, when the steel material is a steel pipe, the tempering time is preferably 15 to 90 minutes. In the steel material having the chemical composition of the present embodiment, those skilled in the art can sufficiently make the yield strength YS within the range of 965 to less than 1069 MPa by appropriately adjusting the holding time at the tempering temperature. It is.

[Quick cooling after tempering]
The cooling after tempering has not been controlled in the past. However, if the cooling rate of the steel material after tempering (that is, after holding the holding time at the tempering temperature) is slow, most of the solid solution C is reprecipitated during the temperature drop. That is, the amount of dissolved C is almost 0% by mass. Therefore, in the present embodiment, the intermediate steel material (element tube) after tempering is rapidly cooled.

Specifically, in the tempering step, an average cooling rate in the range where the surface temperature of the intermediate steel material (element tube) after tempering is 600 to 200 ° C. is defined as a post-tempering cooling rate CR _600-200 . In the method for producing a steel material according to the present embodiment, the post-tempering cooling rate CR _600-200 is 5 ° _C./second or more. Thereby, the amount of solid solution C of this embodiment is obtained. Between 600 ° C. and 200 ° C. is a temperature range where C diffusion is relatively fast. On the other hand, if the cooling rate after tempering is too fast, the C that has been dissolved is hardly precipitated and the amount of dissolved C may be excessive. In this case, the SSC resistance of the steel material decreases. In this case, the low temperature toughness of the steel material may further decrease.

Therefore, the cooling rate CR _600-200 after tempering is 5 to 300 ° _C./second . A preferable lower limit of the cooling rate CR _600-200 after tempering is 10 ° _C./second , more preferably 15 ° _C./second . A preferable upper limit of the cooling rate CR _600-200 after tempering is 100 ° _C./second , more preferably 50 ° _C./second .

The cooling method for _{setting the} cooling rate CR _600-200 after tempering to 5 to 300 ° _C./second is not particularly limited, and may be a well-known method. In the cooling method, for example, the raw tube is continuously forcedly cooled from the tempering temperature, and the surface temperature of the raw tube is continuously reduced. As such a continuous cooling process, there are, for example, a method of immersing the raw tube in a water tank and cooling, and a method of accelerating cooling of the raw tube by shower water cooling, mist cooling or forced air cooling. The post-tempering cooling rate CR _600-200 is _measured at a portion that is cooled most slowly in the cross section of the tempered intermediate steel material (for example, the center portion of the intermediate steel material thickness when both surfaces are forcedly cooled).

In the manufacturing method described above, a method for manufacturing a steel pipe has been described as an example. However, the steel material according to the present embodiment may be a steel plate or other shapes. An example of a manufacturing method of a steel plate or other shapes also includes, for example, a preparation process, a quenching process, and a tempering process, as in the above-described manufacturing method. However, the above-described manufacturing method is an example and may be manufactured by other manufacturing methods.

180 kg of molten steel having the chemical composition shown in Table 1 was produced.

An ingot was manufactured using the above molten steel. The ingot was hot-rolled to produce a steel plate having a thickness of 20 mm.

The steel plate of each steel number after hot rolling was allowed to cool and the steel plate temperature was room temperature (25 ° C.).

After standing to cool, the steel plates of each test number were reheated to bring the steel plate temperature to the quenching temperature (920 ° C., which becomes an austenite single phase region), and soaked for 20 minutes. After soaking, the steel plate was immersed in a water bath and quenched. At this time, the quenching cooling rate (CR _800-500 ) was 400 ° C./min. Test number 23 was soaked in an oil bath after soaking at the quenching temperature. At this time, the average cooling rate between 800 ° C. and 500 ° C. was 40 ° C./min.

After quenching, a tempering treatment was performed on the steel plates of each test number. In the tempering treatment, the tempering temperature was adjusted so as to be an API standard 140 ksi class (yield strength was 965 to 1069 MPa). After performing the heat treatment at each tempering temperature, it was cooled. For cooling, controlled cooling of mist water cooling was performed from both sides of the steel plate. In addition, a sheath type K thermocouple was inserted in advance in the center of the plate thickness of the steel plate, and the temperature was measured for tempering and subsequent cooling. Table 2 shows the tempering temperature (° C.), the tempering time (min), and the cooling rate after tempering (CR _600-200 ) (° _C./second ). The A _c1 points of the steel materials of test numbers 1 to 25 were all 750 ° C., and the tempering temperature was set lower than the A _c1 point.

[Evaluation test]
[YS and TS test]
The tensile test was performed according to ASTM E8. A round bar tensile test piece having a diameter of 6.35 mm and a parallel part length of 35 mm was produced from the center of the thickness of the steel plate of each test number after the above quenching and tempering treatment. The axial direction of the tensile specimen was parallel to the rolling direction of the steel plate. Using each round bar test piece, a tensile test was carried out at room temperature (25 ° C.) and in the atmosphere to obtain a yield strength YS (MPa) and a tensile strength TS (MPa) at each position. In this example, the stress at 0.65% elongation obtained in the tensile test was defined as YS of each test number. The maximum stress during uniform elongation was defined as TS. The ratio of YS and TS was taken as the yield ratio YR (%).

[Microstructure judgment test]
Regarding the microstructure of the steel plates of each test number, except for test numbers 23 and 25, YS was 965 to 1069 MPa (140 ksi class) and YR was 90% or more, so the total volume ratio of tempered martensite and tempered bainite is It was judged that it was 90% or more. In Test No. 23, it is considered that ferrite was generated.

[Solution C content measurement test]
About the steel plate of each test number, the amount of solid solution C (mass%) was measured and computed by the above-mentioned measuring method. The TEM was JEM-2010 manufactured by JEOL Ltd., the acceleration voltage was 200 kV, and the EDS point analysis was performed with an irradiation current of 2.56 nA and measurement at each point for 60 seconds. The observation area | region by TEM was 8 micrometers x 8 micrometers, and observed by arbitrary 10 visual fields. Table 3 shows the residual amount of each element and the concentration in cementite used in the calculation of the solid solution C amount.

[DCB test]
A DCB test based on NACE TM0177-2005 Method D was performed on the steel plates of each test number, and the SSC resistance was evaluated. Specifically, three DCB test pieces shown in FIG. 2A were collected from the thickness center of each steel plate. The DCB specimen was collected so that the longitudinal direction was parallel to the rolling direction. Further, the wedge shown in FIG. 2B was produced from the steel plate. The wedge thickness t was 3.10 mm.

A wedge was driven between the arms of the DCB specimen. Thereafter, the DCB test piece into which the wedge was driven was sealed in a container. A solution prepared by mixing degassed 5% saline and 4 g / L Na acetate and adjusting the pH to 3.5 with hydrochloric acid was poured into the container so that a gas portion remained in the container. Thereafter, a mixed gas of 10% H ₂ S gas and 90% CO ₂ gas was sealed in the autoclave at a total pressure of 1 atm, the liquid phase was stirred, and this mixed gas was saturated with the solution.

After the container having undergone the above steps was closed, the solution was stirred and kept at 24 ° C. for 3 weeks while continuously blowing the mixed gas. Thereafter, the DCB test piece was taken out from the container.

A pin was inserted into the hole formed at the arm tip of each DCB test piece taken out, the notch was opened with a tensile tester, and the wedge release stress P was measured. Furthermore, the notch of the DCB test piece was released in liquid nitrogen, and the crack propagation length a during immersion was measured. The crack propagation length a was measured visually using a caliper. Based on the obtained wedge release stress P and the crack _propagation length a, the fracture toughness value K 1 _SSC (MPa√m) was determined using Equation (6). Fracture toughness values K 1 _SSC (MPa√m) of three DCB specimens were determined for each steel. The arithmetic average of the three fracture toughness values for each steel was defined as the fracture toughness value K 1 _SSC (MPa√m) for that steel.

In Equation (6), h is the height (mm) of each arm of the DCB specimen, B is the thickness (mm) of the DCB specimen, and Bn is the web thickness (mm) of the DCB specimen. is there. These are specified in NACE TM0177-96 Method D.

Table 2 shows the obtained fracture toughness value K 1 _SSC for each test number. When the above-defined fracture toughness value K 1 _SSC value was 30.0 MPa√m or more, it was judged that the SSC resistance was good. In addition, the space _| interval of the arm at the time of driving a wedge before being immersed in a test tank influences _K1SSC value. Therefore, the distance between the arms was measured with a micrometer, and it was confirmed that it was within the API standard range.

[Test results]
Table 2 shows the test results.

Referring to Tables 1 and 2, the chemical compositions of the steel plates with test numbers 1 to 13 were appropriate, YS was 965 to 1069 MPa (140 ksi class), and YR was 90% or more. Further, the amount of solute C was 0.010 to 0.060% by mass. As a result, the K 1 _SSC value was 30.0 MPa√m or more, and excellent SSC resistance was exhibited.

On the other hand, in the steel plates of test numbers 14 and 15, the cooling rate after tempering was too slow. Therefore, the amount of solute C was less than 0.010% by mass. As a result, the fracture toughness value K 1 _SSC was less than _30.0 MPa√m, and excellent SSC resistance was not exhibited.

In the steel plate of test number 16, the tempering time was too short. Therefore, the amount of solute C exceeded 0.060% by mass. As a result, the fracture toughness value K 1 _SSC was less than _30.0 MPa√m, and excellent SSC resistance was not exhibited.

In the steel plate of test number 17, the cooling rate after tempering was too fast. Therefore, the amount of solute C exceeded 0.060% by mass. As a result, the fracture toughness value K 1 _SSC was less than _30.0 MPa√m, and excellent SSC resistance was not exhibited.

In the steel plate of test number 18, the Cr content was too low. As a result, the fracture toughness value K 1 _SSC was less than _30.0 MPa√m, and excellent SSC resistance was not exhibited.

In the steel plate of test number 19, the Mo content was too low. As a result, the fracture toughness value K 1 _SSC was less than _30.0 MPa√m, and excellent SSC resistance was not exhibited.

In the steel plate of test number 20, the Mn content was too high. As a result, the fracture toughness value K 1 _SSC was less than _30.0 MPa√m, and excellent SSC resistance was not exhibited.

In the steel plate of test number 21, the N content was too high. As a result, the fracture toughness value K 1 _SSC was less than _30.0 MPa√m, and excellent SSC resistance was not exhibited.

In the steel plate of test number 22, the Si content was too high. As a result, the fracture toughness value K 1 _SSC was less than _30.0 MPa√m, and excellent SSC resistance was not exhibited.

In the steel plate of test number 23, YR was less than 90%. As a result, the fracture toughness value K 1 _SSC was less than _30.0 MPa√m, and excellent SSC resistance was not exhibited. This is probably because ferrite was mixed into the structure because the cooling rate during quenching was slow.

In the steel plate of test number 24, the cooling rate after tempering was too slow. Therefore, the amount of solute C was less than 0.010% by mass. As a result, the fracture toughness value K 1 _SSC was less than _30.0 MPa√m, and excellent SSC resistance was not exhibited.

In the steel plate of test number 25, the tempering temperature was too low. Therefore, YS exceeded 1069 MPa. As a result, the fracture toughness value K 1 _SSC was less than _30.0 MPa√m, and excellent SSC resistance was not exhibited.

The embodiment of the present invention has been described above. However, the above-described embodiment is merely an example for carrying out the present invention. Therefore, the present invention is not limited to the above-described embodiment, and can be implemented by appropriately changing the above-described embodiment without departing from the spirit thereof.

The steel material according to the present invention is widely applicable to steel materials used in sour environments, preferably used as oil well steel materials used in oil well environments, and more preferably, casings, tubing, line pipes and the like. It can be used as a steel pipe for oil wells.

Claims

% By mass
C: more than 0.50 to 0.80%,
Si: 0.05 to 1.00%,
Mn: 0.05 to 1.00%
P: 0.025% or less,
S: 0.0100% or less,
Al: 0.005 to 0.100%,
Cr: 0.20 to 1.50%,
Mo: 0.25 to 1.50%,
Ti: 0.002 to 0.050%,
B: 0.0001 to 0.0050%,
N: 0.002 to 0.010%,
O: 0.0100% or less,
V: 0 to 0.30%,
Nb: 0 to 0.100%,
Ca: 0 to 0.0100%,
Mg: 0 to 0.0100%,
Zr: 0 to 0.0100%,
Co: 0 to 0.50%,
W: 0 to 0.50%,
Ni: 0 to 0.50%, and
Cu: 0 to 0.50% contained, the balance having a chemical composition consisting of Fe and impurities,
Containing 0.010 to 0.060 mass% of solid solution C,
A steel material having a yield strength of 965 to 1069 MPa and a yield ratio of 90% or more.
The steel material according to claim 1,
The chemical composition is
V: 0.01 to 0.30%, and
Nb: a steel material containing at least one selected from the group consisting of 0.002 to 0.100%.
The steel material according to claim 1 or claim 2,
The chemical composition is
Ca: 0.0001 to 0.0100%,
Mg: 0.0001 to 0.0100%, and
Zr: a steel material containing one or more selected from the group consisting of 0.0001 to 0.0100%.
The steel material according to any one of claims 1 to 3,
The chemical composition is
Co: 0.02 to 0.50%, and
W: a steel material containing at least one selected from the group consisting of 0.02 to 0.50%.
The steel material according to any one of claims 1 to 4,
The chemical composition is
Ni: 0.02 to 0.50%, and
Cu: A steel material containing at least one selected from the group consisting of 0.01 to 0.50%.
The steel material according to any one of claims 1 to 5, wherein the steel material is an oil well steel pipe.
A preparation step of preparing an intermediate steel material having the chemical composition according to any one of claims 1 to 5;
A quenching step of cooling the intermediate steel material at 800 to 1000 ° C. at a cooling rate of 50 ° C./min or more after the preparation step;
A tempering step in which the intermediate steel material after quenching is held at 660 ° C. to Ac 1 point for 10 to 90 minutes, and then cooled at an average cooling rate between 600 ° C. and 200 ° C. at 5 to 300 ° C./sec. Steel manufacturing method.
It is a manufacturing method of the steel materials according to claim 7,
The preparation step includes a material preparation step of preparing a material having the chemical composition according to any one of claims 1 to 5.
And a hot working process for producing an intermediate steel material by hot working the material.