EP3425076B1

EP3425076B1 - Low-alloy, high-strength seamless steel pipe for oil country tubular goods

Info

Publication number: EP3425076B1
Application number: EP16892416.5A
Authority: EP
Inventors: Mitsuhiro Okatsu; Masao YUGA; Yasuhide Ishiguro; Hiroki Ota
Original assignee: JFE Steel Corp
Current assignee: JFE Steel Corp
Priority date: 2016-02-29
Filing date: 2016-11-18
Publication date: 2021-11-10
Anticipated expiration: 2036-11-18
Also published as: AR107720A1; BR112018017250B1; EP3425076A4; EP3425076A1; MX2018010363A; US20190048444A1; WO2017149571A1; BR112018017250A2; NZ744668A

Description

Technical Field

The present invention relates to a high strength seamless steel pipe for oil country tubular goods or gas well, which is excellent in sulfide stress corrosion cracking resistance (SSC resistance) especially in a hydrogen sulfide-containing sour environment. The term "high strength" referred to herein refers to a case of having a strength of 861 MPa or more (125 ksi or more) in terms of yield strength.

Background Art

In recent years, from the viewpoints of a substantial increase in prices of crude oil and expected drying up of oil resources in the near future, the development of a high-depth oil field which has hitherto been disregarded, or an oil field or gas field, etc. in a severe corrosive environment that is a so-called sour environment containing hydrogen sulfide, etc. is eagerly performed. Steel pipes for oil country tubular goods which are used in such an environment are required to have such a material quality that they have both high strength and excellent corrosion resistance (sour resistance).
In response to such a requirement, for example, PTL 1 discloses a steel for oil country tubular goods having excellent sulfide stress corrosion cracking resistance, which is composed of a low alloy steel containing C: 0.2 to 0.35%, Cr: 0.2 to 0.7%, Mo: 0.1 to 0.5%, and V: 0.1 to 0.3% in terms of weight%, and in which the total amount of precipitated carbides and the proportion of an MC type carbide thereamong are prescribed.
In addition, PTL 2 discloses a steel material for oil country tubular goods having excellent sulfide stress corrosion cracking resistance, which contains C: 0.15 to 0.30%, Si: 0.05 to 1.0%, Mn: 0.10 to 1.0%, P: 0.025% or less, S: 0.005% or less, Cr: 0.1 to 1.5%, Mo: 0.1 to 1.0%, Al: 0.003 to 0.08%, N: 0.008% or less, B: 0.0005 to 0.010%, and Ca + O (oxygen) : 0.008% or less in terms of mass%, and further contains one or more selected from Ti: 0.005 to 0.05%, Nb: 0.05% or less, Zr: 0.05% or less, and V: 0.30% or less, and in which with respect to properties of inclusions in steel, a maximum length of continuous non-metallic inclusions and the number of grains having a diameter of 20 µm or more are prescribed.
In addition, PTL 3 discloses a steel for oil country tubular goods having excellent sulfide stress corrosion cracking resistance, which contains C: 0.15 to 0.35%, Si: 0.1 to 1.5%, Mn: 0.1 to 2.5%, P: 0.025% or less, S: 0.004% or less, sol.Al: 0.001 to 0.1%, and Ca: 0.0005 to 0.005% in terms of mass%, and in which a Ca-based non-metallic inclusion composition and a composite oxide of Ca and Al are prescribed, and the hardness of the steel is prescribed by HRC.
The sulfide stress corrosion cracking resistance of steel as referred to in the technologies disclosed in these PTLs 1 to 3 means the presence or absence of the generation of SSC when immersing a round bar tensile specimen in a test bath described in NACE (an abbreviation of National Association of Corrosion Engineering) TM0177 for 720 hours while loading a specified stress according to the NACE TM0177 method A. On the other hand, in recent years, for the purpose of securing more safety of steel pipes for oil country tubular goods, a stress intensity factor K_ISSC value a hydrogen sulfide-containing sour environment obtained by carrying out the DCB (double cantilever beam) test as prescribed according to the NACE TM0177 method D is being demanded to satisfy a prescribed value or more. The above-described prior art does not disclose a specific countermeasure for enhancing such a K_ISSC value.
Meanwhile, PTL 4 discloses a low alloy steel for oil country tubular goods pipe with excellent sulfide stress corrosion cracking resistance having a yield strength of 861 MPa or more, which contains, in terms of mass%, C: 0.2 to 0.35%, Si: 0.05 to 0.5%, Mn: 0.05 to 1.0%, P: 0.025% or less, S: 0.01% or less, Al: 0.005 to 0.10%, Cr: 0.1 to 1.0%, Mo: 0.5 to 1.0%, Ti: 0.002 to 0.05%, V: 0.05 to 0.3%, B: 0.0001 to 0.005%, N: 0.01% or less, and O: 0.01% or less, and in which an equation between a half-value width of the [211] crystal face and a hydrogen diffusion coefficient is prescribed to a predetermined value. This patent literature also describes the above-described K_ISSC values in the working examples. Further low alloy steels for oil well are disclosed in JP 2014 129594 A , US 2006/016520 A1 and EP 1 785 501 A1 .

Citation List

Patent Literature

PTL 1: JP-A-2000-178682
PTL 2: JP-A-2001-172739
PTL 3: JP-A-2002-60893
PTL 4: JP-A-2005-350754

Summary of Invention

Technical Problem

However, almost all of the K_ISSC values in the working examples of PTL 4 are concerned with an aqueous solution of (5 mass% sodium chloride + 0.5 mass% acetic acid) as saturated with a hydrogen sulfide gas at 0.1 atm (= 0.01 MPa) (referred to as "bath A"). However, PTL 4 does not describe any working example for a steel having a yield strength exceeding 861 MPa, which is concerned with an aqueous solution of (5 mass% sodium chloride + 0.5 mass% acetic acid) as saturated with a hydrogen sulfide gas at 1 atm (= 0.1 MPa) (referred to as "bath B"). In general, with respect to the sulfide stress corrosion cracking resistance, it is known that the larger the hydrogen sulfide gas saturated partial pressure, the higher the sensitivity is. In the well environment of a high hydrogen sulfide gas saturated condition, which will be developed in the future, there still remains uncertainty in the use as a low alloy steel pipe for oil country tubular goods having a yield strength of 861 MPa or more as described above.
In view of the foregoing problem, the present invention has been made, and an object thereof is to provide a low alloy high strength seamless steel pipe for oil country tubular goods, which has excellent sulfide stress corrosion cracking resistance (SSC resistance) in a high hydrogen sulfide gas saturated environment, specifically a sour environment having a hydrogen sulfide gas partial pressure of 0.02 MPa or less, while having a high strength of 861 MPa or more in terms of yield strength, and specifically, stably shows a high K_ISSC value.

Solution to Problem

In order to solve the foregoing problem, the present inventors first collected every three or more DCB specimens having a thickness of 10 mm, a width of 25 mm, and a length of 100 mm from seamless steel pipes having various chemical compositions and micro structures of steel and having a yield strength of 861 MPa or more on the basis of the NACE TM0177 method D and provided for a DCB test. As a test bath of the DCB test, a mixed aqueous solution of (0.5 mass% CH₃COOH + CH₃COONa) of 24°C as saturated with a hydrogen sulfide gas of 0.2 atm (0.02 MPa) was used. The DCB specimens into which a wedge had been introduced under a predetermined condition were immersed in this test bath for 336 hours, a length of a crack generated in the DCB specimens during the immersion and a lift-off load P were then measured, and K_ISSC (MPa√m) was calculated according to the following equation (2). $K_{ISSC} = \{Pa (2 \sqrt 3 + 2.36 h/a) {(B/Bn)}^{1 \sqrt 3}\} {/Bh}^{3 / 2}$
Here, Fig. 1 is a schematic view of a DCB specimen. As shown in Fig. 1, h is a height of each arm of the DCB specimen; B is a thickness of the DCB specimen; and B_n is a web thickness of the DCB specimen. For these, numerical values prescribed in the NACE TM0177 method D were used. A target of the K_ISSC value was set to 26.4 MPa√m or more (24 ksi√inch or more) from a supposed maximum notch defect of oil country tubular goods and applied load condition. A graph resulting from sorting the obtained K_ISSC values with an average hardness (Rockwell C scale hardness) of the seamless steel pipe provided with a specimen is shown in Fig. 2. It was noted that though the K_ISSC values obtained by the DCB test tend to decrease with an increase of the hardness of the seamless steel pipe, the numerical values are largely scattered even at the same hardness.
Furthermore, when attention is paid to a chemical composition of steel, it was noted that even at the same hardness, in steel species having the Mo content of 1.1% or more, the K_ISSC value exhibits a higher value. However, some steel species having the Mo content of 1.1% or more were still unsatisfied with the target 26.4 MPa√m or more as a minimum value of scattering.
As a result of extensive and intensive investigations regarding a cause of this scattering, it was determined that a degree of the scattering is different depending upon a stress-strain curve obtained when measuring the yield strength of steel pipe. Fig. 3 shows examples of the stress-strain curve. In the two stress-strain curves of steel pipe (a solid line A and a broken line B) shown in Fig. 3, though the stress values at a strain of 0.5 to 0.7% corresponding to the yield stress do not vary, one of them (broken line B) reveals continuous yielding, whereas the other (solid line A) reveals an upper yield point. Then, it was found that in the steel revealing the stress-strain curve (broken line B) of continuous yielding type, the scattering in the K_ISSC value is large. The present inventors further made extensive and intensive investigations and sorted the dimensions of the scattering in the K_ISSC value by a value (σ_0.7/σ_0.4) as a ratio of a stress (σ_0.7) at a strain of 0.7% to a stress (σ_0.4) at a strain of 0.4% in a stress-strain curve. As a result, it was found that as shown in Fig. 4, by regulating the ( σ_0.7/σ_0.4) of seamless steel pipe to 1.02 or less, the scattering in the K_ISSC value can be reduced to approximately half as compared with the case where the (σ_0.7/σ_0.4) is more than 1.02.
Here, what the scattering in the K_ISSC value is reduced to approximately half means that in a hardness-K_ISSC value correlation, the hardness of steel as a lower limit of the scattering in the K_ISSC value extends to the high hardness side. Specifically, in Fig. 4, in the case where the ( σ_0.7/σ_0.4) of the steel pipe exceeds 1.02 (see white circles in the drawing), even when the Rockwell C scale hardness is a low value as 30.2, values lower than 26.4 MPa√m as a target K_ISSC value are generated, whereas in the case where the ( σ_0.7/σ_0.4) of the steel pipe is 1.02 or less (see black circles in the drawing), even when the Rockwell C scale hardness is a high value as 31.2, 26.4 MPa√m may be satisfied. That is, even when highly strengthened, a high K_ISSC value can be stably obtained.
In the light of the above, there was obtained such a finding that a high K_ISSC value can be stably obtained while highly strengthening a seamless steel pipe to be used in a hydrogen sulfide-containing sour environment. As for the reason why when a value of the ratio of the stress (σ_0.7) at a strain of 0.7% to the stress (σ_0.4) at a strain of 0.4% in the stress-strain curve of seamless steel pipe is low, a high K_ISSC value can be stably obtained, the following reason may be thought. That is, when a stress is given in a state where an initial notch is present as in the DCB test, there is a possibility that plastic deformation is caused at an end of the notch, and in the case where plastic deformation is caused, the sensitivity to sulfide stress corrosion cracking increases. On the other hand, as shown in Fig. 3, when the ( σ_0.7/σ_0.4) is high, namely in a strain region of 0.4 to 0.7%, in the case of a steel having such tensile properties that continuous yielding is not yet revealed, plastic deformation of a notched end can be inhibited. Thus, the sensitivity to sulfide stress corrosion cracking does not change, and a high K_ISSC value is stably obtained.
In order to stably regulate the (σ_0.7/σ_0.4) of seamless steel pipe to 1.02 or less, in addition to limitation of a chemical composition of steel as described later, it is required to regulate a micro structure of steel to martensite such that the stress-strain curve is not made a continuous yielding type, to suppress the formation of a micro structure other than martensite as far as possible, and further to increase a quenching temperature during quenching to solid-solve Mo as far as possible for the purpose of increasing a secondary precipitation amount of Mo. With respect to the above-described secondary precipitation amount, precipitated Mo having been precipitated before quenching is defined as a primary precipitate, and precipitated Mo that is solid-solved during quenching and precipitated after tempering is defined as a secondary precipitate.
Meanwhile, in order to increase the σ_0.4 value, it is required to subject the crystal grains to grain refining, and conversely, the quenching temperature is preferably lower. In order to make the both compatible with each other, in producing a seamless steel pipe, first, the rolling finishing temperature of hot rolling for forming a steel pipe is increased, and after finishing of rolling, direct quenching (also referred to as "DQ"; DQ refers to the matter that at the finishing stage of hot rolling, quenching is immediately performed from a state where the steel pipe temperature is still high) is applied. That is, when the rolling finishing temperature is increased to once solid-solve Mo as far as possible, and thereafter, the quenching temperature during quenching and tempering heat treatment of steel pipe is lowered, both the increase of the above-described secondary precipitation amount of Mo and the grain refining of the micro structure are made compatible with each other, whereby the (σ_0.7/σ_0.4) can be stably regulated to 1.02 or less. In addition, after hot rolling of steel pipe, in the case where DQ is not applicable, by performing the quenching and tempering heat treatment plural times, in particular, by making the initial quenching temperature high as 1,000°C or higher, the effect of DQ can be substituted.
The present invention has been accomplished on the basis of such findings and has the gist as specified in the appended claim.
The term "high strength" as referred to herein refers to a strength of 861 MPa or more (125 ksi or more) in terms of yield strength. Although an upper limit value of the yield strength is not particularly limited, it is preferably 960 MPa.
The low alloy high strength seamless steel pipe for oil country tubular goods of the present invention is excellent in sulfide stress corrosion cracking resistance (SSC resistance). What the sulfide stress corrosion cracking resistance is excellent refers to the matter that when a DCB test using, as a test bath, a mixed aqueous solution of 0.5 mass% of CH₃COOH and CH₃COONa of 24°C as saturated with a hydrogen sulfide gas of 0.2 atm (0.02 MPa), that is a DCB test according to the NACE TM0177 method D, is performed three times, K_ISSC obtained according to the above-described equation (2) is stably 26.4 MPa√m or more in all of the three-times test.

Advantageous Effects of Invention

In accordance with the present invention, it is possible to provide a low alloy high strength seamless steel pipe for oil country tubular goods having excellent sulfide stress corrosion cracking resistance (SSC resistance) in a high hydrogen sulfide gas saturated environment, specifically a sour environment having a hydrogen sulfide gas partial pressure of 0.02 MPa or less, while having a high strength of 861 MPa or more in terms of yield strength, and specifically, stably showing a high K_ISSC value.

Brief Description of Drawings

Fig. 1 is a schematic view of a DCB specimen.
Fig. 2 is a graph showing a relation between hardness and K_ISSC value of a steel pipe.
Fig. 3 is a graph showing a stress-strain curve of steel pipes having a different scattering in the K_ISSC value.
Fig. 4 is a graph showing the matter that by regulating (σ_0.7/σ_0.4) obtained from the stress-strain curve of steel pipe to 1.02 or less, a scattering in the K_ISSC value decreases.

Description of Embodiments

The steel pipe of the present invention is a low alloy high strength seamless steel pipe for oil country tubular goods as defined in the claim.
First of all, the reason for limiting the chemical composition of the steel pipe of the present invention is described. The term "mass%" is hereinafter referred to simply as "%" unless otherwise indicated.

C: 0.25 to 0.31%

C has a function of increasing the strength of steel and is an important element for securing the desired strength. In order to realize high strengthening to such an extent that the yield strength is 861 MPa or more, it is required to contain C of 0.25% or more. On the other hand, when the content of C exceeds 0.31%, a remarkable increase of (σ_0.7/σ_0.4) as described later is caused, and a scattering in the K_ISSC value becomes large. For this reason, the content of C is limited to 0.25 to 0.31%. The content of C is preferably 0.27% or more, and preferably 0.30% or less.

Si: 0.01 to 0.35%

Si is an element functioning as a deoxidizer and having a function of increasing the strength of steel upon being solid-solved in steel and suppressing rapid softening during tempering. In order to obtain such an effect, it is required to contain Si of 0.01% or more. On the other hand, when the content of Si exceeds 0.35%, coarse oxide-based inclusions are formed, and a scattering in the K_ISSC value becomes large. For this reason, the content of Si is limited to 0.01 to 0.35%, and preferably 0.01 to 0.04%.

Mn: 0.45 to 0.70%

Mn is an element having a function of increasing the strength of steel through an improvement in quenching hardenability and of preventing grain boundary embrittlement to be caused due to S by bonding to S and fixing S as MnS. In the present invention, it is required to contain Mn of 0.45% or more. On the other hand, when the content of Mn exceeds 0.70%, a remarkable increase of (σ_0.7/σ_0.4) is caused, and a scattering in the K_ISSC value becomes large. For this reason, the content of Mn is limited to 0.45 to 0.70%. The content of Mn is preferably 0.50% or more, and preferably 0 . 65% or less.

P: 0.010% or less

P shows a tendency to segregate in grain boundaries or the like in a solid-solution state and to cause grain boundary embrittlement cracking or the like, and is thus desirably decreased in amount as far as possible. However, the content of up to 0.010% is permissible. Thus, the content of P is limited to 0.010% or less.

S: 0.001% or less

S is mostly present as sulfide-based inclusions in steel and deteriorates ductility, toughness, and corrosion resistance, such as sulfide stress corrosion cracking resistance, etc. There is a case where S is partially present in a solid-solution state; in this case, however, S shows a tendency to segregate in grain boundaries or the like and to cause grain boundary embrittlement cracking or the like. Thus, it is desired to decrease S as far as possible. However, an excessive decrease in amount rapidly increases smelting costs. Thus, in the present invention, the content of S is limited to 0.001% or less at which adverse effects are permissible.

O (oxygen): 0.0015% or less

O (oxygen) is an inevitable impurity and is present as oxides of Al, Si, and so on in the steel. In particular, when the number of coarse oxides thereof is large, a scattering in the K_ISSC value is caused to become large. For this reason, the content of O (oxygen) is limited to 0. 0015% or less at which adverse effects are permissible. The content of O (oxygen) is preferably 0.0010% or less.

Al: 0.015 to 0.080%

Al functions as a deoxidizer and contributes to a decrease of solid-solved N by bonding to N to form AlN. In order to obtain such an effect, it is required to contain Al of 0.015% or more. On the other hand, when the content of Al exceeds 0.080%, oxide-based inclusions increase, thereby making a scattering in the K_ISSC value large. For this reason, the content of Al is limited to 0.015 to 0.080%. The content of Al is preferably 0.05% or more, and preferably 0.07% or less.

Cu: 0.02 to 0.09%

Cu is an element having a function of improving the corrosion resistance, and when a minute amount thereof is added, a dense corrosion product is formed, the formation and growth of pits serving as a starting point of SSC are suppressed, and the sulfide stress corrosion cracking resistance is remarkably improved. Thus, in the present invention, it is required to contain Cu of 0.02% or more. On the other hand, when the content of Cu exceeds 0.09%, the hot workability during a production process of seamless steel pipe is deteriorated. For this reason, the content of Cu is limited to 0.02 to 0.09%. The content of Cu is preferably 0.03% or more, and preferably 0.05% or less.

Cr: 0.8 to 1.5%

Cr is an element which contributes to an increase in the strength of steel through an improvement in quenching hardenability and improves the corrosion resistance. In addition, Cr bonds to C to form carbides, such as M₃C-based, M₇C₃-based, and M₂₃C₆-based carbides, etc., during tempering. In particular, the M₃C-based carbide improves resistance of softening by tempering of steel, decreases a change in strength to be caused due to tempering, and contributes to an improvement of the yield strength. In order to achieve the yield strength of 861 MPa or more, it is required to contain Cr of 0.8% or more. On the other hand, even when the content of Cr exceeds 1.5%, the effect is saturated, so that such is economically disadvantageous. For this reason, the content of Cr is limited to 0.8 to 1.5%. The content of Cr is preferably 0.9% or more, and preferably 1.1% or less.

Mo: 1.1 to 1.6%

Mo is an element which contributes to an increase in the strength of steel through an improvement in quenching properties and improves the corrosion resistance. With respect to this Mo, the present inventors paid attention especially to a point of forming an M₂C-based carbide. Then, the present inventors have found that the M₂C-based carbide to secondarily have precipitated after tempering improves the resistance of softening by tempering of steel, decreases a change in strength to be caused due to tempering, contributes to an improvement of the yield strength, and converts the shape of stress-strain curve of steel from a continuous yielding type to a yielding type. In particular, in the present invention, as a result of extensive and intensive investigation made by the present inventors, it has been noted that a specified amount of Mo is effective for making both high yield strength and K_ISSC value compatible with each other in the above-described sour environment having a hydrogen sulfide gas partial pressure of 0.2 atm (0.02 MPa) or more. In order to obtain such an effect, it is required to contain Mo of 1.1% or more. On the other hand, when the content of Mo exceeds 1.6%, the Mo₂C-based carbide becomes coarse and serves as a starting point of the sulfide stress corrosion cracking, thereby rather causing a decrease of the K_ISSC value. For this reason, the content of Mo is limited to 1.1 to 1.6%. The content of Mo is preferably 1.2% or more, and preferably 1.5% or less.

V: 0.01 to 0.06%

V is an element which forms a carbide or a nitride and contributes to strengthening of steel. In order to obtain such an effect, it is required to contain V of 0.01% or more. On the other hand, when the content of V exceeds 0.06%, a V-based carbide is coarsened and becomes a starting point of the sulfide stress corrosion cracking, thereby rather causing a decrease of the K_ISSC value. For this reason, the content of V is limited to 0.01 to 0.06%. The content of V is preferably 0 . 03% or more, and preferably 0.05% or less.

Nb: 0.005 to 0.015%

Nb is an element which delays recrystallization in an austenite (γ) temperature region to contribute to refining of γ grains and significantly functions in refining of a lower substructure (for example, a packet, a block, or a lath) of steel immediately after quenching. In order to obtain such an effect, it is required to contain Nb of 0.005% or more. On the other hand, even when the content of Nb exceeds 0.015%, the effect is saturated. For this reason, the content of Nb is limited to 0.005 to 0.015%. The packet as referred to herein is defined as a region composed of a group of laths arranged in parallel and having the same habit plane, and the block is composed of a group of parallel laths having the same orientation. The content of Nb is preferably 0.009% or more.

B: 0.0015 to 0.0030%

B is an element which contributes to an improvement in quenching hardenability at a slight content, and in the present invention, it is required to contain B of 0.0015% or more. On the other hand, even when the content of B exceeds 0.0030%, the effect is saturated, or conversely, a desired effect cannot be expected due to the formation of a Fe boride (Fe-B), so that such is economically disadvantageous. For this reason, the content of B is limited to 0.0015 to 0.0030%. The content of B is preferably 0.0020% to 0.0030%.

Ti: 0.005 to 0.020%

Ti forms a nitride and decreases excessive N in the steel, thereby making the above-described effect of B effective. In addition, Ti is an element which contributes to prevention of coarsening to be caused due to a pinning effect of austenite grains at the time of quenching of steel. In order to obtain such an effect, it is required to contain Ti of 0.005% or more. On the other hand, when the content of Ti exceeds 0.020%, the formation of a coarse MC-type nitride (TiN) is accelerated during casting, resulting in rather coarsening of austenite grains during quenching. For this reason, the content of Ti is limited to 0.005 to 0.020%. The content of Ti is preferably 0.008% or more, and preferably 0.015% or less.

N: 0.005% or less

N is an inevitable impurity in steel and bonds to an element which forms a nitride of Ti, Nb, Al, or the like, to form an MN-type precipitate. Furthermore, excessive N remaining after forming such a nitride also bonds to B to form a BN precipitate. On this occasion, the effect for improving quenching properties due to the addition of B is lost, and therefore, it is preferred that the excessive N is decreased as far as possible. The content of N is limited to 0.005% or less.

Ratio of Ti content to N content (Ti/N): 3.0 to 4.0

In order that both the pinning effect of austenite grains due to the formation of a TiN nitride by the addition of Ti and the effect for improving quenching hardenability due to the addition of B through prevention of the BN formation due to suppression of excessive N may be made compatible with each other, the Ti/N is prescribed. In the case where the Ti/N is lower than 3.0, the excessive N is generated, and BN is formed, so that the solid-solved B during quenching is insufficient. As a result, the micro structure at the finishing of quenching becomes a multi-phase structure of martensite and bainite, or martensite and ferrite, and the stress-strain curve after tempering such a multi-phase structure becomes a continuous yielding type, whereby the value of (σ_0.7/σ_0.4) largely increases. On the other hand, in the case where the Ti/N exceeds 4.0, the pinning effect of austenite grains is deteriorated due to coarsening of TiN, and the required fine grain structure is not obtained. For this reason, the Ti/N is limited to 3.0 to 4.0.
The balance other than the above-described components is Fe and inevitable impurities. In addition to the above-described basic composition, one or more selected from W: 0.1 to 0.2% and Zr: 0.005 to 0.03% may be selected and contained, if desired. In addition to the above, Ca of 0.0005 to 0.0030% may be contained, and the number of oxide-based non-metallic inclusions in steel comprising of Ca and Al and having a maximum bulk size of 5 µm or more, whose composition ratio satisfies a relation: (CaO)/(Al₂O₃) ≥ 4.0, in terms of mass%, is 20 or less per 100 mm².

W : 0.1 to 0.2%

Similar to Mo, W forms a carbide to contribute to an increase in strength due to precipitation hardening, and segregates, in a solid solution, in prior-austenite grain boundaries, thereby contributing to an improvement in the sulfide stress corrosion cracking resistance. In order to obtain such an effect, it is desired to contain W of 0.1% or more. However, when the content of W exceeds 0.2%, the resistance to sulfide stress corrosion cracking is deteriorated. For this reason, in the case where W is contained, the content of W is limited to 0.1 to 0.2%.

Zr: 0.005 to 0.03%

Similar to Ti, Zr forms a nitride and is effective for suppressing the growth of austenite grains during quenching due to a pinning effect. In order to obtain the required effect, it is desired to contain Zr of 0.005% or more. On the other hand, even when the content of Zr exceeds 0.03%, the effect is saturated. For this reason, in the case where Zr is contained, the content of Zr is limited to 0.005 to 0.03%.

Ca: 0.0005 to 0.0030%

Ca is effective for preventing nozzle clogging at the time of continuous casting. In order to obtain the required effect, it is desired to contain Ca of 0.0005% or more. On the other hand, Ca forms an oxide-based non-metallic inclusion complexed with Al, and in particular, in the case where the content of Ca exceeds 0.0030%, a large number of coarse oxide-based non-metallic inclusions are present, thereby deteriorating the sulfide stress corrosion cracking resistance. Specifically, in view of the fact that inclusions in which a composition ratio of the Ca oxide (CaO) to the Al oxide (Al₂O₃) satisfies the equation (1) in terms of mass% especially give adverse effects, it is desired to regulate the number of inclusions having a maximum bulk size of 5 µm or more and satisfying the equation (1) to 20 or less per 100 mm². The number of inclusions can be calculated in the following manner. That is, from an optional one place in the circumferential direction of an end of a steel pipe, a sample for scanning electron microscope (SEM) of a longitudinal orthogonal cross section of the pipe is collected, and with respect to this sample, at least three places of the pipe outer surface, thick-wall center, and inner surface are subjected to SEM observation of inclusions, a chemical composition is analyzed with a characteristic X-ray analyzer annexed to the SEM, and the number of inclusions is calculated from the analysis results. For this reason, in the case where Ca is contained, the content of Ca is limited to 0.0005 to 0.0030% . In addition, in this case, the number of oxide-based non-metallic inclusions in steel comprising of Ca and Al and having a maximum bulk size of 5 µm or more, whose composition ratio satisfies, in terms of mass%, the following equation (1), is limited to 20 or less per 100 mm². The content of Ca is preferably 0.0010% or more, and preferably 0.0016% or less. $(CaO) / ({Al}_{2} O_{3}) \geq 4.0$
The above-described number of inclusions can be controlled by controlling the charged amount of Al at the time of Al-killed treatment to be performed after finishing of decarburization refining and the addition of Ca in an amount in conformity with the analyzed values of Al, O, and Ca in molten steel before the addition of Ca.
In the present invention, though it is not particularly needed to limit the production method of a steel pipe raw material having the above-described composition, it is preferred that a molten steel having the above-described composition is refined by a usually known refining method using a converter, an electric furnace, a vacuum melting furnace, or the like and formed into a steel pipe raw material, such as a billet, etc., by a usual method, such as a continuous casting method, an ingot making-blooming method, etc. The steel pipe raw material is formed into a seamless steel pipe by means of hot forming. In the hot forming method, after piercer perforation, the steel pipe raw material is formed in a predetermined thickness by any method of mandrel mill rolling and plug mill rolling, and thereafter, hot rolling is performed until appropriate diameter-reducing rolling. In order to stably regulate the (σ_0.7/σ_0.4) to 1.02 or less, it is desired to carry out direct quenching (DQ) after hot rolling. Furthermore, it is required to prevent occurrence of the matter that when the micro structure at the finishing of this DQ becomes a multi-phase structure of martensite and bainite, or martensite and ferrite, after the subsequent quenching and tempering heat treatment, the crystal grain diameter of steel and the secondary precipitation amount of Mo or the like become heterogeneous, whereby the value of (σ_0.7/σ_0.4) exceeds 1.02. For that reason, in order that the commencement of DQ may be performed from an austenite single phase region, the finishing temperature of hot rolling is preferably at 950°C or higher. On the other hand, the finishing temperature of DQ is preferably 200°C or lower. After forming the seamless steel pipe, in order to achieve the target yield strength of 861 MPa or more, quenching (Q) and tempering (T) of the steel pipe are carried out. At this time, from the viewpoint of grain refining of crystal grains, the quenching temperature is preferably set to 930°C or lower. On the other hand, in the case where the quenching temperature is lower than 860°C, solid-solution of Mo or the like is insufficient, so that the secondary precipitation amount after finishing of the subsequent tempering cannot be secured. For this reason, the quenching temperature is preferably set to 860 to 930°C. In order to avoid re-transformation of austenite, the tempering temperature is required to be an Ac₁ temperature or lower; however, when it is lower than 600°C, the secondary precipitation amount of Mo or the like cannot be secured. For this reason, it is preferred to set the tempering temperature to at least 600°C or higher.
After hot rolling, in the case where DQ is not applicable, by performing quenching and tempering plural times, in particular, by setting the initial quenching temperature to 950°C or higher, the effect of DQ can be substituted.
Next, the reason for limiting the mechanical properties of the steel pipe of the present invention is described.
The value (σ_0.7/σ_0.4), as a ratio of a stress (σ_0.7) at a strain of 0.7% to a stress (σ_0.4) at a strain of 0.4% in the stress-strain curve, is 1.02 or less.
As described previously, the scattering in the K_ISSC value is largely different according to the shape of the stress-strain curve of steel. The present inventors made extensive and intensive investigations regarding this point. As a result, it has been found that in the case where the value (σ_0.7/σ_0.4), as a ratio of a stress (σ_0.7) at a strain of 0.7% to a stress (σ_0.4) at a strain of 0.4% in the stress-strain curve, is 1.02 or less, the scattering in the K_ISSC value is reduced to approximately half. For this reason, in the present invention, the (σ_0.7/σ_0.4) is limited to 1.02 or less.
In the present invention, the yield strength, the stress (σ_0.4) at a strain of 0.4%, and the stress (σ_0.7) at a strain of 0.7% can be measured by the tensile test in conformity with JIS Z2241.
In addition, though the micro structure of the present invention is not particularly limited, so long as the structure is composed of martensite as a major phase, with the balance being one or more structures of ferrite, residual austenite, perlite, bainite, and the like in an area ratio of 5% or less, the object of the invention of the present application can be achieved.

EXAMPLE 1

The present invention is hereunder described in more detail by reference to Examples.
A steel of each of compositions shown in Table 1 was refined by the converter method and then continuously cast to prepare a bloom slab. This bloom slab was formed into a billet having a round cross section by means of hot rolling. Furthermore, this billet was used as a raw material, heated at a billet heating temperature shown in Table 2, and then hot-rolled by Mannesmann piercing - plug mill rolling - diameter-reducing process, and rolling was finished at a rolling finishing temperature shown in Tables 2 and 3, thereby forming a seamless steel pipe. The steel pipe was cooled to room temperature (35°C or lower) by means of direct quenching (DQ) or air cooling (0.2 to 0.5°C/s) and then heat treated under a heat treatment condition of steel pipe shown in Tables 2 and 3 (Q1 temperature: first quenching temperature, T1 temperature: first tempering temperature, Q2 temperature: second quenching temperature, and T2 temperature: second tempering temperature) . A tensile specimen and DCB specimens were each collected from an optional one place in the circumferential direction of an end of the pipe at the stage of finishing of final tempering. The three or more DCB specimens were respectively collected from every steel pipes.
Using the collected tensile specimen, yield strength, a stress (σ_0.4) at a strain of 0.4%, and a stress (σ_0.7) at a strain of 0.7% were measured by performing the tensile test in conformity with JIS Z2241.
In addition, using the collected DCB specimens, the DCB test was carried out in conformity with the NACE TM0177 method D. As a test bath of the DCB test, a mixed aqueous solution of (0.5 mass% CH₃COOH + CH₃COONa) of 24°C as saturated with a hydrogen sulfide gas of 0.2 atm (0.02 MPa) was used. The DCB specimens into which a wedge had been introduced under a predetermined condition were immersed in this test bath for 336 hours, a length a of a crack generated in the DCB specimens during the immersion and a wedge opening stress P were then measured, and K_ISSC (MPa√m) was calculated according to the following equation (2).
In the case where the yield strength was 861 MPa or more, such was judged to be accepted. In addition, in the case where in all of the three DCB specimens, the K_ISSC value was 26.4 MPa√m or more, such was judged to be accepted. $K_{ISSC} = \{Pa (2 \sqrt 3 + 2.36 h/a) {(B/Bn)}^{1 \sqrt 3}\} {/Bh}^{3 / 2}$
Here, h is a height of each arm of the DCB specimen; B is a thickness of the DCB specimen; and B_n is a web thickness of the DCB specimen. For these, numerical values prescribed in the NACE TM0177 method D were used (see Fig. 1).

[Table 3]

Table 3

Steel pipe No.	Steel No.	Ti/N	Pipe thickness (mm)	Outer diameter (mm)	Steel pipe rolling condition			Steel pipe heat treatment condition				Yield strength (MPa)	σ_0.4	σ_0.7	σ_0.7 /σ_0.4	K_ISSC (MPa√ m)	Remark
Steel pipe No.	Steel No.	Ti/N	Pipe thickness (mm)	Outer diameter (mm)	Billet heating (°C)	Finishing of rolling (°C)	Cooling after rolling	Q1 temperature (°C)	T1 temperature (°C)	Q2 temperature (°C)	T2 temperature (°C)	Yield strength (MPa)	σ_0.4	σ_0.7	σ_0.7 /σ_0.4	K_ISSC (MPa√ m)	Remark
8	G	4.0	13.8	244.5	1261	1022	DQ	911	658	-	-	833	823	831	1.01	28.3	Comparison
																29.3
																31.5
9	H	3.8	13.8	244.5	1262	1023	DQ	911	659	-	-	855	845	853	1.01	27.7	Comparison
																29.4
																30.9
10	I	3.5	13.8	244.5	1261	1028	DQ	910	665	-	-	857	847	855	1.01	27.4	Comparison
																29.5
																30.9
11	J	3.6	13.8	244.5	1264	1022	DQ	909	662	-		871	870	870	1.00	23.8	Comparison
																24.9
																26.2
12	K	3.5	13.8	244.5	1263	1039	DQ	899	688	-	-	916	922	915	0.99	23.4	Comparison
																24.3
																25.9
13	L	34	138	244.5	1259	1031	DQ	910	663	-	-	886	847	889	1.05	23.7	Comparison
																26.1
																30.0
14	M	39	13.8	244.5	1261	1027	DQ	1011	657	-	-	862	816	865	1.06	24.4	Comparison
																25.7
																30.3
15	N	2.8	138	244.5	1265	1033	DQ	912	661	-	-	869	837	870	1.04	24.6	Comparison
																26.0
																30.5

Steel pipe No.	Steel Ti/N No.		Pipe thickness (mm)	Outer diameter (mm)	Steel pipe rolling condition			Steel pipe heat treatment condition				Yield strength (MPa)	(σ_0.4	σ_0.7	σ_0.7 /σ_0.4	K_ISSC (Mpa√ m)	Remark
Steel pipe No.	Steel Ti/N No.		Pipe thickness (mm)	Outer diameter (mm)	Billet Finishing heating of rolling (°C)		Cooling after rolling	Q1 temperature (°C)	T1 temperature (°C)	Q2 temperature (°C)	T2 temperature (°C)	Yield strength (MPa)	(σ_0.4	σ_0.7	σ_0.7 /σ_0.4	K_ISSC (Mpa√ m)	Remark
16	O	4.7	13.8	244.5	1264	1029	DQ	910	664	-	-	893	861	895	1.04	24.1	Comparison
																26.6
																29.9
17	A	3.7	13.8	244.5	1257	1014	DQ	886	596	-	-	922	849	925	1.09	21.7	Comparison
																22.8
																25.5
18	A	3.7	13.8	244.5	1262	1033	DQ	848	653	-	-	872	817	874	1.07	24.9	Comparison
																25.8
																31.1
19	A	3.7	13.8	244.5	1253	1026	Air cooling	896	666	-	-	888	863	889	1.03	25.4	Comparison
																27.1
																29.6

The underlined portions fall outside the scope of the present invention.

In all of the steel pipes 1 to 7 which fall within the scope of the present invention in terms of the chemical composition and (σ_0.7/σ_0.4), the yield strength was 861 MPa or more, and so far as the DCB test bath was a mixed aqueous solution of (0.5 mass% CH₃COOH + CH₃COONa) of 24°C as saturated with a hydrogen sulfide gas of 0.2 atm (0.02 MPa), all of the K_ISSC values obtained in the DCB test of every three specimens satisfied the target 26.4 MPa√m or more without causing scattering.
On the other hand, all of Comparative Example 8 (steel No. G) in which the C amount of the chemical composition was lower than the lower limit of the scope of the present invention, Comparative Example 9 (steel No. H) in which the Mn amount was lower than the lower limit of the scope of the present invention, and Comparative Example 10 (steel No. I) in which the Cr amount was lower than the lower limit of the scope of the present invention could not achieve the target yield strength of 861 MPa or more.
In Comparative Example 11 (steel No. J) in which the Mo amount of the chemical composition was lower than the lower limit of the scope of the present invention and Comparative Example 12 (steel No. K) in which the Mo amount was conversely more than the upper limit of the scope of the present invention, all of the three specimens in the DCB test did not satisfy the target 26.4 MPa√m or more.
In addition, in Comparative Example 13 (steel No. L) in which the Nb amount of the chemical composition was lower than the lower limit of the scope of the present invention and Comparative Example 14 (steel No. M) in which the B amount was lower than the lower limit of the scope of the present invention, the (σ_0.7/σ_0.4) fell outside the scope of the present invention. As a result, the K_ISSC value was largely scattered, and two of the three specimens in the DCB test did not satisfy the target 26.4 MPa√m or more.
In Comparative Example 15 (steel No. N) in which the Ti/N ratio was lower than the lower limit of the scope of the present invention, the (σ_0.7/σ_0.4) fell outside the scope of the present invention. As a result, the K_ISSC value was largely scattered, and two of the three specimens in the DCB test did not satisfy the target 26.4 MPa√m or more.
On the other hand, in Comparative Example 16 (steel No. O) in which the Ti/N ratio exceeded the upper limit of the scope of the present invention, the (σ_0.7/σ_0.4) fell outside the scope of the present invention. As a result, the K_ISSC value was largely scattered, and one of the three specimens in the DCB test did not satisfy the target 26.4 MPa√m or more.
In Comparative Example 17 in which though the chemical composition was compatible with the scope of the present invention, the final tempering temperature was low, the (σ_0.7/σ_0.4) fell outside the scope of the present invention. As a result, all of the three specimens in the DCB test did not satisfy the target 26.4 MPa√m or more. In addition, similarly, in Comparative Example 18 in which the quenching temperature before the final tempering was low, the (σ_0.7/σ_0.4) fell outside the scope of the present invention. As a result, the K_ISSC value was largely scattered, and two of the three specimens in the DCB test did not satisfy the target 26.4 MPa√m or more. In Comparative Example 19 in which the direct quenching (DQ) was not performed, and the quenching and tempering heat treatment of steel pipe was performed only one time, the (σ_0.7/σ_0.4) fell outside the scope of the present invention. As a result, the K_ISSC value was largely scattered, and one of the three specimens in the DCB test did not satisfy the target 26.4 MPa√m or more.

EXAMPLE 2

A steel of each of compositions shown in Table 4 was ingoted by the converted method and then continuously cast to prepare a bloom slab. This bloom slab was formed into a billet having a round cross section by means of hot rolling. Furthermore, this billet was used as a raw material, heated at a billet heating temperature shown in Table 5, and then subjected to Mannesmann piercing - plug mill rolling - diameter-reducing rolling while heated, and rolling was finished at a rolling finishing temperature shown in Table 5, thereby forming a seamless steel pipe. The steel pipe was cooled to room temperature (35°C or lower) by means of direct quenching (DQ) or air cooling (0.2 to 0.5°C/s) and then heat treated under a heat treatment condition of steel pipe shown in Table 5 (Q1 temperature: first quenching temperature, T1 temperature: first tempering temperature, Q2 temperature: second quenching temperature, and T2 temperature: second tempering temperature). A sample for SEM of a longitudinal orthogonal cross section, a tensile specimen, and DCB specimens were each collected from an optional one place in the circumferential direction of an end of the pipe at the stage of finishing of final tempering. The three or more DCB specimens were respectively collected from every steel pipes.
With respect to the collected sample for SEM, three places of the pipe outer surface, thick-wall center, and inner surface were subjected to SEM observation of inclusions, a chemical composition was analyzed with a characteristic X-ray analyzer annexed to the SEM, and the number (per mm²) of oxide-based non-metallic inclusions in steel comprising of Ca and Al and having a major diameter of 5 µm or more and satisfying the equation (1) was calculated. $(CaO) / ({Al}_{2} O_{3}) \geq 4.0$
In addition, using the collected tensile specimen, a yield strength, a stress (σ_0.4) at a strain of 0.4%, and a stress (σ_0.7) at a strain of 0.7% were measured by the performing tensile test in conformity with JIS Z2241.
In addition, using the collected DCB specimens, the DCB test was carried out in conformity with the NACE TM0177 method D. As a test bath of the DCB test, a mixed aqueous solution of (0.5 mass% CH₃COOH + CH₃COONa) of 24°C as saturated with a hydrogen sulfide gas of 0.2 atm (0.02 MPa) was used. The DCB specimens into which a wedge had been introduced under a predetermined condition were immersed in this test bath for 336 hours, a length a of a crack generated in the DCB specimen during the immersion and a wedge opening stress P were then measured, and K_ISSC (MPa√m) was calculated according to the foregoing equation (2).
In the case where the yield strength was 861 MPa or more, such was judged to be accepted. In addition, in the case where in all of the three DCB specimens, the K_ISSC value was 26.4 MPa√m or more, such was judged to be accepted.

[Table 4]

[Table 5]

Table 5

Steel pipe No.	Steel No.	Ti /N	Number of inclusions (per/100mm²) (*1)	Pipe thickness (mm)	Outer diameter (mm)	Steel pipe rolling condition			Steel pipe heat treatment condition				Yield strength (MPa)	σ_0.4	σ_0.7	σ_0.7 /σ_0.4	K_ISSC (MPa√m)	Remark
Steel pipe No.	Steel No.	Ti /N	Number of inclusions (per/100mm²) (*1)	Pipe thickness (mm)	Outer diameter (mm)	Billet heating (°C)	Finishing of rolling (°C)	Cooling after rolling	Q1 temperature (°C)	T1 temperature (°C)	Q2 temperature (°C)	T2 temperature (°C)	Yield strength (MPa)	σ_0.4	σ_0.7	σ_0.7 /σ_0.4	K_ISSC (MPa√m)	Remark
2-1	P	3.0	0	13.8	244.5	1241	1018	DQ	880	663	-	-	905	908	903	0.99	27.2	Invention
																	28.8
																	31.4
2-2	Q	3.5	1	24.0	177.8	1267	1112	DQ	889	668	-	-	885	883,	883	1.00	27.7	Invention
																	28.4
																	32.1
2-3	R	3.1	6	24.0	177.8	1271	1109	DQ	890	652	-	-	879	871	880	1.01	26.8	Invention
																	27.3
																	294
2-4	S	3.1	1	13.8	244.5	1259	1031	Air cooling	1010	700	890	647	899	880	898	1.02	26.6	Invention
																	26.8
																	29.1
2-5	I	3.51	82	13.8	244.5	1239	1021	DQ	891	661	-	-	899	882	900	1.02	23.2	Comparison
																	26.7
																	28.1
2-6	U	3.2	26	13.8	244.5	1238	1017	DQ	893	659	-	-	894	889	896	1.01	25.5	Comparison
																	27.4
																	29.6

The underlined portions fall outside the scope of the present invention.
∗1) Number (per 100 mm²) of oxide-based non-metallic inclusions in steel satisfying a relation: (CaO)/(Al₂O₃) ≥ 4.0 and having a major diameter of 5 µm or more.

In all of the steel pipes 2-1 to 2-4 which fall within the scope of the present invention in terms of the chemical composition, the number of inclusions, and (σ_0.7/σ_0.4), the yield strength was 861 MPa or more, and all of the K_ISSC values obtained in the DCB test of every three specimens satisfied the target 26.4 MPa√m or more without causing scattering.
On the other hand, in Comparative Example 2-5 (steel No. T) in which the upper limit of Ca was more than the upper limit of the scope of the present invention, the K_ISSC value was largely scattered, and one of the three specimens in the DCB test did not satisfy the target 26.4 MPa√m or more. In addition, in Comparative Example 2-6 (steel No. U), the addition of Ca was performed without taking into consideration the state where the Ca amount in the molten steel before the addition of Ca was high due to Ca as an impurity contained in the alloyed iron of other elements added at the time of secondary refining. For that reason, though the Ca amount fell within the scope of the present invention, the number of oxide-based non-metallic inclusions in steel comprising of Ca and Al and having a major diameter of 5 µm or more and satisfying the equation (1) was more than the upper limit of the scope of the present invention, the K_ISSC value was largely scattered, and one of the three specimens in the DCB test did not satisfy the target 26.4 MPa√m or more.

Claims

A low alloy high strength seamless steel pipe for oil country tubular goods having a composition containing, in terms of mass%,
C: 0.25 to 0.31%,

Si: 0.01 to 0.35%,

Mn: 0.45 to 0.70%,

P: 0.010% or less,

S: 0.001% or less,

O: 0.0015% or less,

Al: 0.015 to 0.080%,

Cu: 0.02 to 0.09%,

Cr: 0.8 to 1.5%,

Mo: 1.1 to 1.6%,

V: 0.01 to 0.06%,

Nb: 0.005 to 0.015%,

B: 0.0015 to 0.0030%,

Ti: 0.005 to 0.020%, and

N: 0.005% or less,

and having a value of a ratio of the Ti content to the N content (Ti/N) of 3.0 to 4.0, optionally, one or more selected from, in terms of mass%,

W: 0.1 to 0.2%,

Zr: 0.005 to 0.03%, and

Ca: 0.0005 to 0.0030%,

with the balance being Fe and inevitable impurities,

the steel pipe having a value σ0.7/σ0.4, as a ratio of a stress at a strain of 0.7% to a stress at a strain of 0.4% in a stress-strain curve, of 1.02 or less and a yield strength of 861 MPa or more, whereas the stress at a strain and the yield strength are measured in accordance with JIS Z 2241,

and has the number of oxide-based non-metallic inclusions in steel comprising Ca and Al and having a major diameter of 5 µm or more, whose composition ratio satisfies, in terms of mass%, the following equation (1), of 20 or less per 100 mm²: $(CaO) / ({Al}_{2} O_{3}) \geq 4.0$
wherein equation (1) is satisfied when Ca: 0.0005 to 0.0030% is contained.