WO2022102441A1 - サワー環境での使用に適した鋼材 - Google Patents
サワー環境での使用に適した鋼材 Download PDFInfo
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Definitions
- This disclosure relates to steel materials, and more particularly to steel materials suitable for use in a sour environment.
- oil wells and gas wells By deepening oil wells and gas wells (hereinafter, oil wells and gas wells are collectively referred to simply as "oil wells"), it is required to increase the strength of steel materials for oil wells represented by steel pipes for oil wells.
- 80 ksi class yield strength less than 80 to 95 ksi, that is, 552 to less than 655 MPa
- 95 ksi class yield strength less than 95 to 110 ksi, that is, less than 655 to 758 MPa
- steel pipes for oil wells having a yield strength of 110 ksi or more have begun to be demanded.
- the sour environment means an acidified environment containing hydrogen sulfide.
- carbon dioxide may be contained.
- SSC resistance sulfide Stress Cracking resistance
- Patent Document 1 JP-A-2000-297344
- Patent Document 2 JP-A-2001-2711134
- Patent Document 3 International Publication No. 2008 /. It is proposed in No. 123422 (Patent Document 3).
- the steel for oil wells disclosed in Patent Document 1 has a mass% of C: 0.15 to 0.3%, Cr: 0.2 to 1.5%, Mo: 0.1 to 1%, V: It contains 0.05 to 0.3% and Nb: 0.003 to 0.1%.
- This steel for oil wells has a total amount of precipitated carbides of 1.5 to 4% by mass, a ratio of MC type carbides to the total amount of carbides of 5 to 45% by mass, and M 23 C 6 type carbides. The ratio is (200 / t) mass% or less when the wall thickness of the product is t (mm). It is described in Patent Document 1 that this steel for oil wells has excellent SSC resistance.
- the low alloy steel material disclosed in Patent Document 2 has C: 0.2 to 0.35%, Si: 0.05 to 0.5%, Mn: 0.1 to 1%, P: in mass%. 0.025% or less, S: 0.01% or less, Cr: 0.1 to 1.2%, Mo: 0.1 to 1%, B: 0.0001 to 0.005%, Al: 0.005 Contains ⁇ 0.1%, N: 0.01% or less, V: 0.05 to 0.5%, Ni: 0.1% or less, W: 1.0% or less, O: 0.01% or less
- the balance is Fe and impurities, and the formula (0.03 ⁇ Mo ⁇ V ⁇ 0.3) and the formula (0.5 ⁇ Mo ⁇ V + GS / 10 ⁇ 1) are satisfied, and the yield strength is 1060 MPa or more. ..
- the GS in the formula means the ASTM particle size number of the old austenite grains. It is described in Patent Document 2 that this low alloy steel material has excellent SSC resistance.
- P 0.025% or less
- S 0.010% or less
- N 0.007% or less
- B less than 0.0003%.
- This low alloy steel has M 23 C 6 type precipitates having a grain size of 1 ⁇ m or more and 0.1 pieces / mm 2 or less. It is described in Patent Document 3 that this low alloy steel has improved SSC resistance.
- a steel material having excellent SSC resistance may be obtained by a technique other than the techniques disclosed in Patent Documents 1 to 3.
- An object of the present disclosure is to provide a steel material having excellent SSC resistance in a normal temperature sour environment and a low temperature sour environment.
- the steel materials according to this disclosure are By mass%, C: 0.20 to 0.45%, Si: 1.36 to 3.20%, Mn: 0.02 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: 0.36 to 1.50%, V: 0.01 to 0.90%, Ti: 0.002 to 0.050%, B: 0.0001 to 0.0050%, N: 0.0100% or less, O: 0.0100% or less, Nb: 0 to 0.030%, Ca: 0-0.0100%, Mg: 0 to 0.0100%, Zr: 0-0.0100%, Rare earth elements: 0-0.0100%, Co: 0 to 0.50%, W: 0 to 0.50%, Ni: 0 to 0.50%, Cu: 0 to 0.50%, and The balance consists of Fe and impurities, which satisfies equation (1).
- Yield strength ⁇ YS is 758 MPa or more
- the yield strength ⁇ YS and the dislocation density ⁇ satisfy equation (2).
- the content of the corresponding element is substituted in% by mass into the element symbol in the formula (1).
- the yield strength is substituted in MPa for ⁇ YS in equation (2), and the dislocation density is substituted in m -2 for ⁇ .
- the steel material according to the present disclosure has excellent SSC resistance in a normal temperature sour environment and a low temperature sour environment.
- FIG. 1A is a diagram showing the relationship between the Si content and the dislocation density in the example having a yield strength of 110 ksi class (less than 758 to 862 MPa) in this example.
- FIG. 1B is a diagram showing the relationship between the Si content and the dislocation density in the example having a yield strength of 125 ksi class (862 to less than 965 MPa) in this example.
- FIG. 1C is a diagram showing the relationship between the Si content and the dislocation density in the example having a yield strength of 140 ksi or more (965 MPa or more) in this example.
- FIG. 1A is a diagram showing the relationship between the Si content and the dislocation density in the example having a yield strength of 110 ksi class (less than 758 to 862 MPa) in this example.
- FIG. 1B is a diagram showing the relationship between the Si content and the dislocation density in the example having a yield strength of 125 ksi class (862 to less than 965 MPa) in this example
- FIG. 3 is a side view of the test piece used when determining the A c3 point in this embodiment.
- the present inventors investigated and investigated a method for obtaining excellent SSC resistance in both normal temperature sour environment and low temperature sour environment in steel materials expected to be used in a sour environment. As a result, the present inventors obtained the following findings.
- the present inventors focused on the chemical composition and investigated and examined steel materials having excellent SSC resistance in a normal temperature sour environment and a low temperature sour environment.
- mass% C: 0.20 to 0.45%
- Mn 0.02 to 1.00%
- P 0.025% or less
- S 0.0100% or less
- Al 0.005.
- a steel material having a chemical composition containing Cu: 0 to 0.50% may obtain excellent SSC resistance in a normal temperature sour environment and a low temperature sour environment.
- the yield strength of the steel material is increased.
- dislocations can occlude hydrogen. Therefore, if the dislocation density of the steel material increases, the amount of hydrogen occluded by the steel material may also increase. That is, if the hydrogen concentration in the steel material is increased as a result of increasing the dislocation density, the SSC resistance of the steel material is lowered even if high strength is obtained. Therefore, for example, when the yield strength is increased to 110 ksi or more (758 MPa or more) by increasing the dislocation density, it may not be possible to obtain sufficiently excellent SSC resistance in a normal temperature sour environment and a low temperature sour environment.
- the present inventors examined a method for reducing the dislocation density of a steel material having a yield strength of 110 ksi or more (758 MPa or more) as an example among the above-mentioned chemical compositions. As a result, the present inventors have found that the dislocation density may be reduced even when the yield strength of the steel material is increased to 110 ksi or more (758 MPa or more) by increasing the Si content. .. This point will be specifically described with reference to the drawings.
- FIG. 1A to 1C are diagrams showing the relationship between the Si content and the dislocation density in this embodiment.
- FIG. 1A shows the Si content (mass) of the examples described later, which have the above-mentioned chemical composition and a yield strength of 110 ksi class (758 to less than 862 MPa) and are produced by the preferred production method described later. %) And the dislocation density ⁇ (10 14 m -2 ).
- FIG. 1B shows the Si content (mass) of the examples described later, which have the above-mentioned chemical composition and a yield strength of 125 ksi class (862 to less than 965 MPa) and are produced by the preferred production method described later. %) And the dislocation density ⁇ (10 14 m -2 ).
- FIG. 1A shows the Si content (mass) of the examples described later, which have the above-mentioned chemical composition and a yield strength of 110 ksi class (758 to less than 862 MPa) and are produced by the preferred production method described later.
- 1C shows the Si content (% by mass) of the examples described below having the above-mentioned chemical composition and yield strength of 140 ksi or more (965 MPa or more) and manufactured by the preferable production method described later.
- the dislocation density ⁇ (10 14 m -2 ). The dislocation density ⁇ was determined by using the method described later.
- the dislocation density ⁇ can be increased even if the yield strength is about the same. It can be seen that it tends to decrease. In particular, when the Si content is 1.36% or more, the dislocation density ⁇ is significantly reduced, and there is a possibility that the SSC resistance of the steel material not only in the normal temperature sour environment but also in the low temperature sour environment can be enhanced.
- the steel material has a chemical composition of 50%, W: 0 to 0.50%, Ni: 0 to 0.50%, Cu: 0 to 0.50%, and the balance is Fe and impurities, the dislocation density is high. It was further reduced, and it became clear that excellent SSC resistance may be obtained in a normal temperature sour environment and a low temperature sour environment.
- the present inventors changed the relationship between the dislocation density ⁇ and the yield strength with the steel material having a low Si content. It was found that That is, in the steel material having the above-mentioned chemical composition, even if the dislocation density ⁇ is reduced to the same level as the steel material having a low Si content, excellent SSC resistance may not be obtained particularly in a low temperature sour environment. Therefore, the present inventors have studied in detail how much the dislocation density ⁇ should be reduced in the steel material having the above-mentioned chemical composition to obtain excellent SSC resistance even in a low-temperature sour environment.
- the dislocation density ⁇ and the yield strength ⁇ YS satisfy the following formula (2), so that it is excellent not only in a normal temperature sour environment but also in a low temperature sour environment. It was clarified that SSC resistance can be obtained. 691 ⁇ YS -110 ⁇ ⁇ ⁇ 10 -7 ⁇ 795 (2)
- the yield strength is substituted in MPa for ⁇ YS in Eq. ( 2 )
- the dislocation density is substituted in ⁇ for ⁇ .
- Fn2 ⁇ YS -110 ⁇ ⁇ ⁇ 10 -7 .
- Fn2 is an index showing SSC resistance in a low temperature sour environment. Specifically, in the steel material having the above-mentioned chemical composition, if Fn2 exceeds 691, it has excellent resistance not only in a normal temperature sour environment but also in a low temperature sour environment, provided that the other configurations of the present embodiment are satisfied. SSC property can be obtained.
- the dislocation density ⁇ may not be sufficiently reduced.
- the dislocation density ⁇ and the yield strength ⁇ YS cannot satisfy the equation (2).
- the present inventors increased the Si content to 1.36% or more in the above-mentioned chemical composition, and as a result, the dislocation density ⁇ and the yield strength ⁇ were determined by the balance of the content of each element in the chemical composition. I thought it might be affecting the relationship with YS .
- the dislocation density ⁇ can be stably reduced by satisfying the following formula (1) in addition to the above-mentioned chemical composition.
- the content of the corresponding element is substituted in% by mass into the element symbol in the formula (1).
- Fn1 27 ⁇ Mn + 9 ⁇ Cr-14 ⁇ Mo-770 ⁇ C 2 +760 ⁇ C-11 ⁇ Si 2 +4 ⁇ Si.
- Fn1 is an index showing the balance between the dislocation density ⁇ and the yield strength ⁇ YS in the above-mentioned chemical composition containing a Si content of 1.36% or more. That is, in the steel material according to the present embodiment, in addition to the above-mentioned chemical composition containing a Si content of 1.36% or more, Fn1 is further made higher than 85. As a result, Fn2 can be made larger than 691. This point will be specifically described with reference to the drawings.
- FIG. 2 shows Fn1 and Fn2, and the examples described later, among the examples described later, having the above-mentioned chemical composition and yield strength of 110 ksi or more (758 MPa or more) and manufactured by the preferable production method described later. It was prepared using the evaluation results of the low temperature SSC resistance test evaluated by the above method.
- the dislocation density ⁇ for obtaining Fn2 and the yield strength ⁇ YS were obtained by the method described later.
- ⁇ in FIG. 2 indicates a steel material having excellent SSC resistance in the low temperature SSC resistance test.
- ⁇ in FIG. 2 indicates a steel material that did not have excellent SSC resistance in the low temperature SSC resistance test.
- Fn2 rapidly increases when Fn1 exceeds 85, at least in the range where the yield strength is 110 ksi or more (758 MPa or more). Further, when Fn2 exceeds 691, it is confirmed that the steel material has excellent SSC resistance in a low temperature sour environment. On the other hand, in the steel material having the above-mentioned chemical composition, when Fn1 is 85 or less, Fn2 is 691 or less, and excellent SSC resistance cannot be obtained in a low temperature sour environment.
- the steel material according to the present embodiment has a chemical composition satisfying the formula (1) in addition to the above-mentioned chemical composition, and further, the dislocation density ⁇ and the yield strength ⁇ YS satisfy the formula (2).
- the steel material according to the present embodiment has excellent SSC resistance not only in a normal temperature sour environment but also in a low temperature sour environment even if the yield strength ⁇ YS is 758 MPa or more.
- the gist of the steel material according to this embodiment completed based on the above knowledge is as follows.
- Yield strength ⁇ YS is 758 MPa or more
- the yield strength ⁇ YS and the dislocation density ⁇ satisfy equation (2).
- Steel material. 27 x Mn + 9 x Cr-14 x Mo-770 x C 2 +760 x C-11 x Si 2 +4 x Si> 85 (1) 691 ⁇ YS -110 ⁇ ⁇ ⁇ 10 -7 ⁇ 795 (2)
- the content of the corresponding element is substituted in% by mass into the element symbol in the formula (1).
- the yield strength is substituted in MPa for ⁇ YS in equation (2), and the dislocation density is substituted in m -2 for ⁇ .
- the steel material is a steel pipe for oil wells. Steel material.
- the steel pipe for an oil well may be an oil well pipe.
- the steel pipe for oil wells may be a seamless steel pipe or a welded steel pipe.
- Oil country tubular goods are, for example, steel pipes used in casings and tubing applications.
- the steel pipe for oil wells according to this embodiment is preferably a seamless steel pipe. If the steel pipe for an oil well according to the present embodiment is a seamless steel pipe, it has excellent SSC resistance in a normal temperature sour environment and a low temperature sour environment even if the wall thickness is 15 mm or more.
- the term "normal temperature sour environment” means a sour environment at 10 to 30 ° C.
- the term “low temperature sour environment” means a sour environment of less than 10 ° C.
- Carbon (C) enhances the hardenability of the steel material and enhances the strength of the steel material. C further promotes spheroidization of carbides during tempering during the manufacturing process and enhances the SSC resistance of the steel material. If the carbides are dispersed, the strength of the steel material is further increased. If the C content is too low, the above effect cannot be sufficiently obtained even if the content of other elements is within the range of the present embodiment. On the other hand, if the C content is too high, even if the content of other elements is within the range of the present embodiment, the amount of carbide becomes too large and the toughness of the steel material is lowered. If the C content is too high, quenching cracks may easily occur during quenching during the manufacturing process.
- the C content is 0.20 to 0.45%.
- the lower limit of the C content is preferably 0.22%, more preferably 0.23%, still more preferably 0.24%, still more preferably 0.25%.
- the preferred upper limit of the C content is 0.40%, more preferably 0.38%, still more preferably 0.37%.
- Si 1.36 to 3.20% Silicon (Si) deoxidizes steel. Si further reduces the dislocation density of the steel material and enhances the SSC resistance of the steel material. If the Si content is too low, the above effect cannot be sufficiently obtained even if the content of other elements is within the range of the present embodiment. On the other hand, if the Si content is too high, the SSC resistance of the steel material is lowered even if the content of other elements is within the range of the present embodiment. Therefore, the Si content is 1.36 to 3.20%.
- the preferred lower limit of the Si content is 1.38%, more preferably 1.40%, still more preferably 1.45%, still more preferably 1.50%, still more preferably 1.70%. %.
- the preferred upper limit of the Si content is 3.10%, more preferably 3.00%, still more preferably 2.90%.
- Mn 0.02 to 1.00%
- Manganese (Mn) deoxidizes steel. Mn further enhances the hardenability of steel materials. If the Mn content is too low, the above effect cannot be sufficiently obtained even if the content of other elements is within the range of the present embodiment. On the other hand, if the Mn content is too high, Mn segregates at the grain boundaries together with impurities such as P and S. As a result, even if the content of other elements is within the range of this embodiment, the SSC resistance of the steel material is lowered. Therefore, the Mn content is 0.02 to 1.00%.
- the preferred lower limit of the Mn content is 0.03%, more preferably 0.05%, still more preferably 0.10%.
- the preferred upper limit of the Mn content is 0.90%, more preferably 0.80%, still more preferably 0.70%, still more preferably 0.65%.
- Phosphorus (P) is an impurity. That is, the lower limit of the P content is more than 0%. If the P content is too high, even if the content of other elements is within the range of the present embodiment, P segregates at the grain boundaries and the SSC resistance of the steel material is lowered. Therefore, the P content is 0.025% or less.
- the preferred upper limit of the P content is 0.020%, more preferably 0.015%. It is preferable that the P content is as low as possible. However, an extreme reduction in P content significantly increases manufacturing costs. Therefore, when industrial production is taken into consideration, the preferable lower limit of the P content is 0.0001%, more preferably 0.0003%, still more preferably 0.001%, still more preferably 0.003%. Is.
- S 0.0100% or less Sulfur (S) is an impurity. That is, the lower limit of the S content is more than 0%. If the S content is too high, even if the content of other elements is within the range of the present embodiment, S segregates at the grain boundaries and the SSC resistance of the steel material is lowered. Therefore, the S content is 0.0100% or less.
- the preferred upper limit of the S content is 0.0050%, more preferably 0.0030%. It is preferable that the S content is as low as possible. However, an extreme reduction in S content significantly increases manufacturing costs. Therefore, when industrial production is taken into consideration, the preferable lower limit of the S content is 0.0001%, more preferably 0.0002%, still more preferably 0.0003%.
- Al 0.005 to 0.100%
- Aluminum (Al) deoxidizes steel. If the Al content is too low, even if the content of other elements is within the range of the present embodiment, the above effect cannot be sufficiently obtained, and the SSC resistance of the steel material is lowered. On the other hand, if the Al content is too high, coarse oxide-based inclusions are generated even if the content of other elements is within the range of the present embodiment, and the SSC resistance of the steel material is lowered. Therefore, the Al content is 0.005 to 0.100%.
- the lower limit of the Al content is preferably 0.015%, more preferably 0.020%.
- the preferred upper limit of the Al content is 0.080%, more preferably 0.060%.
- the "Al" content as used herein means "acid-soluble Al", that is, the content of "sol.Al".
- Chromium (Cr) enhances the hardenability of steel materials. Cr further increases the tempering and softening resistance of the steel material, enabling high-temperature tempering. As a result, the SSC resistance of the steel material is improved. If the Cr content is too low, the above effect cannot be sufficiently obtained even if the content of other elements is within the range of the present embodiment. On the other hand, if the Cr content is too high, the SSC resistance of the steel material is lowered even if the content of other elements is within the range of the present embodiment. Therefore, the Cr content is 0.20 to 1.50%.
- the lower limit of the Cr content is preferably 0.25%, more preferably 0.30%, still more preferably 0.35%, still more preferably 0.40%.
- the preferred upper limit of the Cr content is 1.40%, more preferably 1.30%.
- Mo 0.36 to 1.50%
- Molybdenum (Mo) enhances the hardenability of steel materials. Mo further increases the tempering and softening resistance of steel materials, enabling high-temperature tempering. As a result, the SSC resistance of the steel material is improved. If the Mo content is too low, the above effect cannot be sufficiently obtained even if the content of other elements is within the range of the present embodiment. On the other hand, if the Mo content is too high, the above effect will be saturated. Therefore, the Mo content is 0.36 to 1.50%.
- the lower limit of the Mo content is preferably 0.40%, more preferably 0.50%, still more preferably 0.60%.
- the preferred upper limit of the Mo content is 1.40%, more preferably 1.30%, still more preferably 1.25%.
- V 0.01 to 0.90% Vanadium (V) combines with C and / or N to form carbides, nitrides or carbonitrides (hereinafter referred to as "carbonitrides and the like").
- carbonitrides and the like the substructure of the steel material is made finer by the pinning effect, and the SSC resistance of the steel material is enhanced.
- V further increases temper softening resistance and enables high temperature tempering. As a result, the SSC resistance of the steel material is improved. If the V content is too low, the above effect cannot be sufficiently obtained even if the content of other elements is within the range of the present embodiment.
- the V content is 0.01 to 0.90%.
- the lower limit of the V content is preferably 0.02%, more preferably 0.04%, still more preferably 0.06%, still more preferably 0.08%.
- the preferred upper limit of the V content is 0.85%, more preferably 0.80%, still more preferably 0.75%, still more preferably 0.70%, still more preferably 0.60. %, More preferably 0.50%.
- Titanium (Ti) combines with N to form a nitride, and the crystal grains of the steel material are refined by the pinning effect. As a result, the strength of the steel material is increased. If the Ti content is too low, the above effect cannot be sufficiently obtained even if the content of other elements is within the range of the present embodiment. On the other hand, if the Ti content is too high, even if the content of other elements is within the range of this embodiment, the Ti nitride becomes coarse and the SSC resistance of the steel material deteriorates. Therefore, the Ti content is 0.002 to 0.050%.
- the preferred lower limit of the Ti content is 0.003%, more preferably 0.005%.
- the preferred upper limit of the Ti content is 0.040%, more preferably 0.030%, still more preferably 0.020%.
- B Boron (B) dissolves in steel to enhance the hardenability of the steel material and enhance the strength of the steel material. If the B content is too low, the above effect cannot be sufficiently obtained even if the content of other elements is within the range of the present embodiment. On the other hand, if the B content is too high, even if the content of other elements is within the range of the present embodiment, 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 lower limit of the B content is preferably 0.0003%, more preferably 0.0007%.
- the preferred upper limit of the B content is 0.0030%, more preferably 0.0025%, still more preferably 0.0020%, still more preferably 0.0015%.
- N Nitrogen (N) is inevitably contained. That is, the lower limit of the N content is more than 0%. N combines with Ti to form a nitride, and the crystal grains of the steel material are refined by the pinning effect. As a result, the strength of the steel material is increased. However, if the N content is too high, coarse nitrides are formed and the SSC resistance of the steel material is lowered even if the content of other elements is within the range of the present embodiment. Therefore, the N content is 0.0100% or less. The preferred upper limit of the N content is 0.0050%, more preferably 0.0045%. The preferable lower limit of the N content for more effectively obtaining the above effect is 0.0005%, more preferably 0.0010%, still more preferably 0.0015%, still more preferably 0.0020%. Is.
- Oxygen (O) is an impurity. That is, the lower limit of the O content is more than 0%. If the O content is too high, coarse oxides are formed even if the content of other elements is within the range of this embodiment, and the low temperature toughness and SSC resistance of the steel material are lowered. Therefore, the O content is 0.0100% or less.
- the preferred upper limit of the O content is 0.0050%, more preferably 0.0030%, still more preferably 0.0020%. It is preferable that the O content is as low as possible. However, an extreme reduction in O content significantly increases manufacturing costs. Therefore, when industrial production is taken into consideration, the preferable lower limit of the O content is 0.0001%, more preferably 0.0002%, still more preferably 0.0003%.
- the balance of the chemical composition of the steel material according to this embodiment consists of Fe and impurities.
- the impurities are mixed from ore, scrap, or the manufacturing environment as a raw material when the steel material is industrially manufactured, and are within a range that does not adversely affect the steel material according to the present embodiment. Means what is acceptable.
- the chemical composition of the above-mentioned steel material may further contain Nb instead of a part of Fe.
- Niobium (Nb) is an optional element and may not be contained. That is, the Nb content may be 0%. When contained, Nb forms carbonitrides and the like. The carbonitride and the like refine the crystal grains of the steel material by the pinning effect, and enhance the low temperature toughness and SSC resistance of the steel material. Nb further forms fine carbides during tempering to increase the tempering softening resistance of the steel material and increase the strength of the steel material. If even a small amount of Nb is contained, the above effect can be obtained to some extent.
- the Nb content is 0 to 0.030%.
- the preferable lower limit of the Nb content is more than 0%, more preferably 0.002%, still more preferably 0.003%, still more preferably 0.007%.
- the preferred upper limit of the Nb content is 0.025%, more preferably 0.020%.
- the chemical composition of the steel material described above may further contain one or more elements selected from the group consisting of Ca, Mg, Zr, and rare earth elements, instead of a part of Fe. All of these elements are optional elements and detoxify S in the steel material as sulfide. As a result, these elements enhance the SSC resistance of the steel material.
- Ca 0-0.0100% Calcium (Ca) is an optional element and may not be contained. That is, the Ca content may be 0%.
- Ca detoxifies S in the steel material as a sulfide and enhances the SSC resistance of the steel material. If even a small amount of Ca is contained, the above effect can be obtained to some extent. However, if the Ca content is too high, even if the content of other elements is within the range of the present embodiment, the oxide in the steel material becomes coarse and the SSC resistance of the steel material deteriorates. Therefore, the Ca content is 0 to 0.0100%.
- the lower limit of the Ca content is more than 0%, more preferably 0.0001%, still more preferably 0.0003%, still more preferably 0.0006%.
- the preferred upper limit of the Ca content is 0.0040%, more preferably 0.0025%, still more preferably 0.0020%.
- Mg 0 to 0.0100%
- Mg Magnesium
- Mg is an optional element and may not be contained. That is, the Mg content may be 0%.
- Mg detoxifies S in the steel material as a sulfide and enhances the SSC resistance of the steel material. If even a small amount of Mg is contained, the above effect can be obtained to some extent. However, if the Mg content is too high, even if the content of other elements is within the range of the present embodiment, the oxide in the steel material becomes coarse and the SSC resistance of the steel material deteriorates. Therefore, the Mg content is 0 to 0.0100%.
- the lower limit of the Mg content is more than 0%, more preferably 0.0001%, still more preferably 0.0003%, still more preferably 0.0006%.
- the preferred upper limit of the Mg content is 0.0040%, more preferably 0.0025%, still more preferably 0.0020%.
- Zr Zirconium
- Zr Zirconium
- the Zr content may be 0%.
- Zr detoxifies S in the steel material as a sulfide and enhances the SSC resistance of the steel material. If even a small amount of Zr is contained, the above effect can be obtained to some extent. However, if the Zr content is too high, even if the content of other elements is within the range of the present embodiment, the oxide in the steel material becomes coarse and the SSC resistance of the steel material deteriorates. Therefore, the Zr content is 0 to 0.0100%.
- the preferable lower limit of the Zr content is more than 0%, more preferably 0.0001%, still more preferably 0.0003%, still more preferably 0.0006%.
- the preferred upper limit of the Zr content is 0.0040%, more preferably 0.0025%, still more preferably 0.0020%.
- Rare earth element 0 to 0.0100%
- Rare earth elements are optional elements and may not be contained. That is, the REM content may be 0%.
- REM detoxifies S in the steel material as a sulfide and enhances the SSC resistance of the steel material.
- REM further binds to P in the steel material and suppresses segregation of P at the grain boundaries. Therefore, the decrease in SSC resistance of the steel material due to the segregation of P is suppressed. If even a small amount of REM is contained, the above effect can be obtained to some extent even if the content of other elements is within the range of the present embodiment.
- the REM content is 0 to 0.0100%.
- the preferable lower limit of the REM content is more than 0%, more preferably 0.0001%, still more preferably 0.0003%, still more preferably 0.0006%.
- the preferred upper limit of the REM content is 0.0040%, more preferably 0.0025%.
- REM in this specification is a scandium (Sc) of atomic number 21, yttrium (Y) of atomic number 39, and lanthanum (La) of atomic number 57 which is a lanthanoid to atomic number 71. It means one or more elements selected from the group consisting of yttrium (Lu). Further, the REM content in the present specification means the total content of these elements.
- the chemical composition of the above-mentioned steel material may further contain one or more elements selected from the group consisting of Co and W instead of a part of Fe. All of these elements are optional elements and form a protective corrosive film in a sour environment and suppress the intrusion of hydrogen into steel materials. As a result, these elements enhance the SSC resistance of the steel material.
- Co is an optional element and may not be contained. That is, the Co content may be 0%. When contained, Co forms a protective corrosive coating in a sour environment and suppresses the ingress of hydrogen into the steel. This enhances the SSC resistance of the steel material. If even a small amount of Co is contained, the above effect can be obtained to some extent. However, if the Co content is too high, the hardenability of the steel material is lowered and the strength of the steel material is lowered even if the content of other elements is within the range of the present embodiment. Therefore, the Co content is 0 to 0.50%.
- the lower limit of the Co content is preferably more than 0%, more preferably 0.02%, still more preferably 0.03%, still more preferably 0.05%.
- the preferred upper limit of the Co content is 0.45%, more preferably 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 corrosive coating in a sour environment and suppresses the ingress of hydrogen into the steel. This enhances the SSC resistance of the steel material. If W is contained even in a small amount, 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 even if the content of other elements is within the range of the present embodiment, and the low temperature toughness and SSC resistance of the steel material are lowered. Therefore, the W content is 0 to 0.50%.
- the lower limit of the W content is more than 0%, more preferably 0.02%, still more preferably 0.03%, still more preferably 0.05%.
- the preferred upper limit of the W content is 0.45%, more preferably 0.40%.
- the chemical composition of the above-mentioned steel material may further contain one or more elements 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 steel materials.
- Nickel (Ni) is an optional element and may not be contained. That is, the Ni content may be 0%. When contained, Ni enhances the hardenability of the steel material and enhances the strength of the steel material. Ni also dissolves in steel to increase the low temperature toughness of the steel. If even a small amount of Ni is contained, these effects can be obtained to some extent. However, if the Ni content is too high, even if the content of other elements is within the range of this embodiment, local corrosion is promoted and the SSC resistance of the steel material is lowered. Therefore, the Ni content is 0 to 0.50%.
- the lower limit of the Ni content is more than 0%, more preferably 0.01%, still more preferably 0.02%.
- the upper limit of the Ni content is preferably 0.30%, more preferably 0.20%, still more preferably 0.10%.
- 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 enhances the hardenability of the steel material and enhances the strength of the steel material. If even a small amount of Cu is contained, 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 deteriorates even if the content of other elements is within the range of the present embodiment. Therefore, the Cu content is 0 to 0.50%.
- the lower limit of the Cu content is more than 0%, more preferably 0.01%, still more preferably 0.02%, still more preferably 0.05%.
- the preferred upper limit of the Cu content is 0.35%, more preferably 0.25%.
- Fn1 is too low, the dislocation density ⁇ cannot be sufficiently reduced, and Fn2 described later becomes 691 or less.
- Fn1 is larger than 85, the dislocation density ⁇ can be reduced, and Fn2 described later exceeds 691.
- the steel material according to the present embodiment has an Fn1 of more than 85 in addition to the above-mentioned chemical composition.
- the preferred lower limit of Fn1 is 87, more preferably 89, still more preferably 90, still more preferably 91.
- the upper limit of Fn1 is not particularly limited, but in the range of the above-mentioned chemical composition, the upper limit of Fn1 is substantially 207.
- the dislocation density ⁇ and the yield strength ⁇ YS satisfy the following equation (2). 691 ⁇ YS -110 ⁇ ⁇ ⁇ 10 -7 ⁇ 795 (2)
- the yield strength is substituted in MPa for ⁇ YS in Eq. ( 2 )
- the dislocation density is substituted in ⁇ for ⁇ .
- the upper limit of Fn2 is substantially 795 or less. Therefore, in the steel material according to the present embodiment, Fn2 satisfies more than 691 to 795.
- the preferred lower limit of Fn2 is 693, more preferably 694.
- the preferred upper limit of Fn2 is 790, more preferably 785.
- the method for obtaining the yield strength ⁇ YS of the steel material according to this embodiment will be described later.
- the dislocation density ⁇ of the steel material according to this embodiment can be obtained by the following method.
- a test piece for measuring the dislocation density is prepared from the steel material according to the present embodiment.
- the steel material is a steel plate
- the test piece is prepared from the center of the plate thickness.
- the steel material is a steel pipe
- a test piece is prepared from the central part of the wall thickness.
- the steel material is a steel bar having a circular cross section
- a test piece is prepared from the R / 2 position.
- the R / 2 position means the center position of the radius R in the cross section perpendicular to the axial direction of the steel bar.
- the size of the test piece is, for example, 20 mm in width ⁇ 20 mm in length ⁇ 2 mm in thickness.
- the thickness direction of the test piece is the thickness direction of the steel material (plate thickness direction, wall thickness direction, or cross-sectional radial direction of the steel bar).
- the observation surface of the test piece is a surface having a width of 20 mm and a length of 20 mm.
- the observation surface of the test piece is mirror-polished, and then electrolytic polishing is performed using 10% by volume of perchloric acid (acetic acid solvent) to remove the strain on the surface layer.
- the half-value width ⁇ K of the peaks of the (110), (211), and (220) planes of the body-centered cubic structure (iron) was obtained by X-ray diffraction (XRD: X-Ray Diffraction) on the observation surface after electrolytic polishing. demand.
- the half width ⁇ K is measured with the radiation source as CoK ⁇ ray, the tube voltage as 30 kV, and the tube current as 100 mA. Further, in order to measure the full width at half maximum derived from the X-ray diffractometer, LaB 6 (lanthanum hexaboride) powder is used.
- the non-uniform strain ⁇ of the test piece is obtained from the half width ⁇ K obtained by the above method and the Williamson-Hall equation (Equation (3)).
- ⁇ K ⁇ cos ⁇ / ⁇ 0.9 / D + 2 ⁇ ⁇ sin ⁇ / ⁇ (3)
- ⁇ diffraction angle
- ⁇ wavelength of X-ray
- D crystallite diameter
- the dislocation density ⁇ (m -2 ) can be obtained by using the obtained non-uniform strain ⁇ and the equation (4).
- ⁇ 14.4 ⁇ ⁇ 2 / b 2 (4)
- the range of the dislocation density ⁇ is not particularly limited.
- the dislocation density ⁇ may satisfy the equation (2).
- the dislocation density ⁇ in the steel material is 0.1 ⁇ 10 14 (m ⁇ 2 ) or more.
- the dislocation density ⁇ in the steel material is 0.4 ⁇ 10 14 (m ⁇ 2 ) or more.
- the dislocation density ⁇ in the steel material is 2.4 ⁇ 10 14 (m ⁇ 2 ) or more.
- the dislocation density ⁇ in the steel material is less than 2.4 ⁇ 10 14 (m ⁇ 2 ).
- the dislocation density ⁇ in the steel material is less than 6.2 ⁇ 10 14 (m ⁇ 2 ).
- the dislocation density ⁇ in the steel material is 11.8 ⁇ 10 14 (m ⁇ 2 ) or less. That is, when the yield strength ⁇ YS of the steel material is 758 to 1069 MPa, the dislocation density ⁇ of the steel material is 0.1 ⁇ 10 14 to 11.8 ⁇ 10 14 (m ⁇ 2 ).
- the yield strength ⁇ YS of the steel material according to this embodiment is 758 MPa or more.
- the upper limit of the yield strength ⁇ YS is not particularly limited as long as it satisfies Fn2 in relation to the dislocation density ⁇ .
- the yield strength ⁇ YS as used herein means the 0.2% offset proof stress obtained in the tensile test.
- the steel material according to the present embodiment has the above-mentioned chemical composition including the formula (1), and the dislocation density ⁇ and the yield strength ⁇ YS satisfy the above-mentioned formula (2), so that the yield strength ⁇ YS is 758 MPa or more. Even if it is present, it has excellent SSC resistance in a normal temperature sour environment and a low temperature sour environment.
- the yield strength ⁇ YS of the steel material according to the present embodiment can be obtained by the following method. Tensile tests are performed by a method according to ASTM E8 / E8M (2013). A round bar test piece is produced from the steel material according to the present embodiment. When the steel material is a steel plate, a round bar test piece is produced from the center of the plate thickness. When the steel material is a steel pipe, a round bar test piece is prepared from the central part of the wall thickness. When the steel material is a steel bar with a circular cross section, a round bar test piece is manufactured from the R / 2 position. The size of the round bar test piece is, for example, a parallel portion diameter of 4 mm and a gauge point distance of 20 mm.
- the axial direction of the round bar test piece is parallel to the rolling direction of the steel material.
- a tensile test is carried out in the air at room temperature (25 ° C.) using a round bar test piece, and the obtained 0.2% offset proof stress is defined as the yield strength ⁇ YS (MPa).
- the preferable yield strength ⁇ YS of the steel material according to the present embodiment is 758 MPa or more (110 ksi or more). That is, the steel material according to the present embodiment has the above-mentioned chemical composition including the formula (1), and the dislocation density ⁇ and the yield strength ⁇ YS satisfy the above-mentioned formula (2), so that it is 758 MPa or more (110 ksi or more). Even if it has the yield strength of, it has excellent SSC resistance in normal temperature sour environment and low temperature sour environment.
- the upper limit of the yield strength ⁇ YS of the steel material according to the present embodiment is not particularly limited, but is, for example, 1069 MPa (155 ksi).
- the total volume fraction of tempered martensite and tempered bainite is 90% or more.
- the rest of the microstructure is, for example, ferrite or pearlite. If the microstructure of the steel material having the above-mentioned chemical composition contains 90% or more of the total volume fraction of tempered martensite and tempered bainite, the normal temperature sour environment and the normal temperature sour environment are satisfied, provided that the other configurations of the present embodiment are satisfied. Shows excellent SSC resistance in low temperature sour environment. That is, in the present embodiment, if the steel material has excellent SSC resistance, the microstructure determines that the total volume fraction of tempered martensite and tempered bainite is 90% or more.
- a test piece is prepared from a steel material.
- the steel material is a steel plate
- a test piece having an observation surface of 10 mm in the rolling direction and 10 mm in the plate thickness direction is produced from the central portion of the plate thickness.
- the steel material is a steel plate having a thickness of less than 10 mm
- a test piece having an observation surface of the thickness of the steel plate in the rolling direction of 10 mm and the plate thickness direction is cut out.
- the steel material is a steel pipe
- a test piece having an observation surface having an observation surface of 10 mm in the pipe axis direction and 8 mm in the wall thickness (tube diameter) direction from the central portion of the wall thickness is produced.
- the steel material is a steel pipe having a wall thickness of less than 10 mm
- a test piece having an observation surface of the wall thickness of the steel pipe in the pipe axial direction and the pipe diameter direction is cut out.
- the observation surface of the test piece After polishing the observation surface of the test piece to a mirror surface, it is immersed in a nital corrosive solution for about 10 seconds to reveal the structure by etching.
- the etched observation surface is observed in 10 fields with a secondary electron image using a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the visual field area is, for example, 400 ⁇ m 2 (magnification 5000 times).
- tempered martensite and tempered bainite are identified from the contrast.
- the method for obtaining the area ratio is not particularly limited, and a well-known method may be used.
- image analysis can be used to determine the area ratio of tempered martensite and tempered bainite.
- the arithmetic mean value of the area ratios of tempered martensite and tempered bainite obtained in all fields of view is defined as the volume ratio of tempered martensite and tempered bainite.
- the old austenite grain size (former ⁇ grain size) is not particularly limited. Normally, if the old ⁇ grains of the steel material are fine, the yield strength and the SSC resistance are stably increased. Therefore, it is preferable that the old ⁇ grains are fine. On the other hand, in the steel material according to the present embodiment, as described above, the Si content in the chemical composition is increased to 1.36% or more. As a result, the old ⁇ grains tend to be coarse in the microstructure of the steel material.
- the preferred old ⁇ grain size in the microstructure is 35 ⁇ m or less.
- the upper limit of the old ⁇ particle size is more preferably 33 ⁇ m, still more preferably 31 ⁇ m, still more preferably 30 ⁇ m.
- the old ⁇ grains in the microstructure are fine. Therefore, in the steel material according to the present embodiment, the lower limit of the old ⁇ grain size in the microstructure is not particularly limited. In the steel material according to the present embodiment, the lower limit of the old ⁇ grain size in the microstructure is, for example, 5 ⁇ m.
- the old ⁇ particle size can be obtained by the following method.
- the steel material is a steel plate
- a test piece having an observation surface of 10 mm in the rolling direction and 10 mm in the plate thickness direction is cut out from the central portion of the plate thickness.
- the steel material is a steel plate having a thickness of less than 10 mm
- a test piece having an observation surface of the thickness of the steel plate in the rolling direction of 10 mm and the plate thickness direction is cut out.
- the steel material is a steel pipe
- a test piece having an observation surface of 10 mm in the pipe axis direction and 10 mm in the pipe diameter direction is cut out from the central portion of the wall thickness.
- the steel material is a steel pipe having a wall thickness of less than 10 mm
- a test piece having an observation surface of the wall thickness of the steel pipe in the pipe axial direction and the pipe diameter direction is cut out.
- the steel material is a steel bar having a circular cross section
- a test piece including the R / 2 position in the center and having an observation surface of 10 mm in the axial direction and 10 mm in the radial direction in the cross section is cut out.
- the diameter of the cross section is less than 10 mm
- a test piece including the R / 2 position and having an observation surface having an axial direction of 10 mm and a diameter in the radial direction of the cross section is cut out.
- the test piece After embedding the test piece in resin and polishing the observation surface to a mirror surface, immerse it in a saturated aqueous solution of picric acid for about 60 seconds to reveal the old ⁇ grain boundary by etching.
- the etched observation surface is observed in 10 fields with a secondary electron image using an SEM to generate a photographic image. From the generated photographic image, the area of the old ⁇ grain is obtained, and from the obtained area, the diameter equivalent to the circle of the old ⁇ grain is obtained.
- the arithmetic mean value of the circle-equivalent diameter of the old ⁇ grains obtained in 10 fields is defined as the old ⁇ grain size ( ⁇ m).
- the shape of the steel material according to this embodiment is not particularly limited.
- the steel material is, for example, a steel pipe or a steel plate.
- the steel material may be a solid material (steel bar).
- the preferable wall thickness is 9 to 60 mm.
- the steel material according to the present embodiment is a seamless steel pipe.
- the steel material according to the present embodiment is a seamless steel pipe, even a thick seamless steel pipe having a wall thickness of 15 mm or more has excellent SSC resistance in a normal temperature sour environment and a low temperature sour environment.
- the SSC resistance of the steel material according to this embodiment can be evaluated by a normal temperature SSC resistance test and a low temperature SSC resistance test. Both the normal temperature SSC resistance test and the low temperature SSC resistance test are carried out by a method compliant with NACE TM0177-2005 Method A.
- the size of the round bar test piece is, for example, a diameter of 6.35 mm and a length of the parallel portion of 25.4 mm.
- the axial direction of the round bar test piece is parallel to the rolling direction of the steel material.
- a stress corresponding to 95% of the actual yield stress is applied to the round bar test piece.
- a test solution at 24 ° C. is injected into the test container so that the stressed round bar test piece is immersed, and the test bath is used. After degassing the test bath, 1 atm of H2S gas is blown into the test bath to saturate the test bath.
- a test bath infused with 1 atm of H2S gas is held at 24 ° C. for 720 hours.
- a mixed aqueous solution (NACE solution A) of 5.0% by mass sodium chloride and 0.5% by mass acetic acid is used as the test solution.
- a round bar test piece is produced from the steel material according to the present embodiment.
- the steel material is a steel plate
- a round bar test piece is produced from the center of the plate thickness.
- the steel material is a steel pipe
- a round bar test piece is prepared from the central part of the wall thickness.
- the steel material is a steel bar with a circular cross section
- a round bar test piece is manufactured from the R / 2 position.
- the size of the round bar test piece is, for example, a diameter of 6.35 mm and a length of the parallel portion of 25.4 mm.
- the axial direction of the round bar test piece is parallel to the rolling direction of the steel material.
- a stress corresponding to 90% of the actual yield stress is applied to the round bar test piece.
- a test solution at 4 ° C. is injected into the test container so that the stressed round bar test piece is immersed, and the test bath is used. After degassing the test bath, 1 atm of H2S gas is blown into the test bath to saturate the test bath.
- a test bath infused with 1 atm of H2S gas is held at 4 ° C. for 720 hours.
- the yield strength of the steel material according to the present embodiment is less than 758 to 862 MPa
- the steel material has a yield strength of less than 758 to 862 MPa. No cracks are confirmed.
- "cracking is not confirmed” means that cracking is not confirmed when the test piece after the test is observed with the naked eye and a projector having a magnification of 10 times.
- the size of the round bar test piece is, for example, a diameter of 6.35 mm and a length of the parallel portion of 25.4 mm.
- the axial direction of the round bar test piece is parallel to the rolling direction of the steel material.
- a stress corresponding to 95% of the actual yield stress is applied to the round bar test piece.
- a test solution at 24 ° C. is injected into the test container so that the stressed round bar test piece is immersed, and the test bath is used. After degassing the test bath, 1 atm of H2S gas is blown into the test bath to saturate the test bath.
- a test bath infused with 1 atm of H2S gas is held at 24 ° C. for 720 hours.
- a mixed aqueous solution (NACE solution A) of 5.0% by mass sodium chloride and 0.5% by mass acetic acid is used as the test solution.
- a round bar test piece is produced from the steel material according to the present embodiment.
- the steel material is a steel plate
- a round bar test piece is produced from the center of the plate thickness.
- the steel material is a steel pipe
- a round bar test piece is prepared from the central part of the wall thickness.
- the steel material is a steel bar with a circular cross section
- a round bar test piece is manufactured from the R / 2 position.
- the size of the round bar test piece is, for example, a diameter of 6.35 mm and a length of the parallel portion of 25.4 mm.
- the axial direction of the round bar test piece is parallel to the rolling direction of the steel material.
- a stress corresponding to 85% of the actual yield stress is applied to the round bar test piece.
- a test solution at 4 ° C. is injected into the test container so that the stressed round bar test piece is immersed, and the test bath is used. After degassing the test bath, 1 atm of H2S gas is blown into the test bath to saturate the test bath.
- a test bath infused with 1 atm of H2S gas is held at 4 ° C. for 720 hours.
- the yield strength of the steel material according to the present embodiment is less than 862 to 965 MPa
- the steel material has a yield strength of less than 862 to 965 MPa. No cracks are confirmed.
- the size of the round bar test piece is, for example, a diameter of 6.35 mm and a length of the parallel portion of 25.4 mm.
- the axial direction of the round bar test piece is parallel to the rolling direction of the steel material.
- a stress corresponding to 95% of the actual yield stress is applied to the round bar test piece.
- a test solution at 24 ° C. is injected into the test container so that the stressed round bar test piece is immersed, and the test bath is used. After degassing the test bath, a mixed gas of 0.1 atm H 2S gas and 0.9 atm CO 2 gas is blown into the test bath to saturate the test bath.
- a test bath in which a mixed gas of 0.1 atm H 2S gas and 0.9 atm CO 2 gas is blown is held at 24 ° C. for 720 hours.
- a mixed aqueous solution (NACE solution B) of 5.0% by mass sodium chloride and 0.4% by mass sodium acetate adjusted to pH 3.5 with acetic acid is used as a test solution.
- NACE solution B a mixed aqueous solution
- a round bar test piece is produced from the steel material according to the present embodiment.
- the steel material is a steel plate
- a round bar test piece is produced from the center of the plate thickness.
- the steel material is a steel pipe
- a round bar test piece is prepared from the central part of the wall thickness.
- a round bar test piece is manufactured from the R / 2 position.
- the size of the round bar test piece is, for example, a diameter of 6.35 mm and a length of the parallel portion of 25.4 mm.
- the axial direction of the round bar test piece is parallel to the rolling direction of the steel material.
- a stress corresponding to 85% (820 MPa) of 965 MPa is applied to the round bar test piece.
- a test solution at 4 ° C. is injected into the test container so that the stressed round bar test piece is immersed, and the test bath is used. After degassing the test bath, a mixed gas of 0.1 atm H 2S gas and 0.9 atm CO 2 gas is blown into the test bath to saturate the test bath.
- a test bath in which a mixed gas of 0.1 atm H 2S gas and 0.9 atm CO 2 gas is blown is held at 4 ° C. for 720 hours.
- a method for manufacturing a steel material according to this embodiment will be described.
- a method for manufacturing a seamless steel pipe will be described as an example of the steel material according to the present embodiment.
- the method for manufacturing a seamless steel pipe includes a step of preparing a raw pipe (preparation step) and a step of quenching and tempering the raw pipe to make a seamless steel pipe (quenching step and tempering step).
- the manufacturing method according to this embodiment is not limited to the manufacturing method described below. Hereinafter, each step will be described in detail.
- an intermediate steel material having the above-mentioned chemical composition is prepared.
- the method for producing the intermediate steel material is not particularly limited.
- the intermediate steel material referred to here is a plate-shaped steel material when the final product is a steel plate, and is a raw pipe when the final product is a steel pipe.
- the preparation process may include a process of preparing the material (material preparation process) and a process of hot-working the material to produce an intermediate steel material (hot-working process).
- material preparation process a process of preparing the material
- hot-working process a process of hot-working the material to produce an intermediate steel material
- a material is manufactured using molten steel having the above-mentioned chemical composition.
- the method for producing the material is not particularly limited, and a well-known method may be used. Specifically, slabs (slabs, blooms, or billets) may be produced by a continuous casting method using molten steel. An ingot may be manufactured by an ingot method using molten steel. If necessary, slabs, blooms or ingots may be lump-rolled to produce billets.
- the material (slab, bloom, or billet) is manufactured by the above steps.
- the prepared material is hot-worked to produce an intermediate steel material.
- the intermediate steel material corresponds to a raw pipe.
- the billet is heated in a heating furnace.
- the heating temperature is not particularly limited, but is, for example, 1100 to 1300 ° C.
- Hot working is performed on the billets extracted from the heating furnace to manufacture raw pipes (seamless steel pipes).
- the method of hot working is not particularly limited, and a well-known method may be used.
- the Mannesmann method may be carried out as hot working to manufacture a bare tube.
- the round billet is drilled and rolled by a drilling machine.
- the drilling ratio is not particularly limited, but is, for example, 1.0 to 4.0.
- the perforated round billet is further hot-rolled with a mandrel mill, reducer, sizing mill or the like to form a raw pipe.
- the cumulative surface reduction rate in the hot working process is, for example, 20 to 70%.
- raw pipes from billets.
- a raw pipe may be manufactured by forging such as the Erhard method.
- the raw tube is manufactured by the above process.
- the wall thickness of the raw tube is not particularly limited, but is, for example, 9 to 60 mm.
- the raw tube manufactured by hot working may be air-cooled (As-Rolled).
- the raw tube manufactured by hot working may be directly quenched after hot working without being cooled to room temperature, or may be quenched after reheating (reheating) after hot working. good.
- cooling may be stopped or slow cooling may be carried out during quenching. In this case, it is possible to prevent the raw pipe from being cracked.
- the quenching is carried out directly after the hot working or after the heat is supplemented.
- the stress relief annealing may be carried out after the quenching and before the heat treatment in the next step. In this case, the residual stress of the raw pipe is removed.
- the intermediate steel material is prepared in the preparation process.
- the intermediate steel material may be manufactured by the above-mentioned preferable process, and may be manufactured by an intermediate steel material manufactured by a third party, or to a factory other than the factory where the quenching process and the tempering process described later are carried out, or to other business establishments. You may prepare the intermediate steel material manufactured by the above. Hereinafter, the quenching process will be described in detail.
- quenching means quenching an intermediate steel material having A 3 points or more.
- the temperature of the intermediate steel material immediately before quenching when quenching is carried out is also referred to as a quenching temperature. That is, in the present specification, the quenching temperature is the surface temperature of the intermediate steel material measured by a thermometer installed on the outlet side of the apparatus for performing the final hot working when the quenching is performed directly after the hot working. Corresponds to.
- the quenching temperature further corresponds to the temperature of the furnace in which the reheating or reheating is performed when the quenching is performed after the heating or reheating after the hot working.
- the points A c3 and the points Ar 3 are collectively referred to as “A 3 points”.
- a 3 points when direct quenching is carried out after hot working, the intermediate steel material is rapidly cooled from a quenching temperature of Ar 3 points or more.
- quenching is performed by reheating the intermediate steel material once cooled after hot working, the intermediate steel material is rapidly cooled from the quenching temperature of 3 points or more.
- the Si content is increased to reduce the dislocation density ⁇ of the steel material.
- the Si content is simply increased , the A3 point of the steel material may become too high. If the A3 point of the steel material is too high , the quenching temperature must be raised, and the old ⁇ grains become coarse. If the old ⁇ grains become coarse in the intermediate steel material after quenching, the dislocation density ⁇ cannot be sufficiently reduced in the tempering step described later. As a result, the dislocation density ⁇ and the yield strength ⁇ YS cannot satisfy the equation (2), and the SSC resistance of the steel material is lowered.
- Fn1 is an index of A3 point. If Fn1 exceeds 85, it is possible to prevent the A3 point from becoming too high. As a result, it is not necessary to raise the quenching temperature too high, so that the coarsening of the old ⁇ grains can be suppressed. As a result, by carrying out a preferable tempering in the tempering step described later, the dislocation density ⁇ and the yield strength ⁇ YS can satisfy the formula (2) in the steel material after the tempering step described later.
- the preferred quenching temperature is 860 to 1000 ° C. If the quenching temperature is too low, the effect of quenching cannot be sufficiently obtained, and the mechanical properties specified in the present embodiment cannot be obtained in the manufactured steel material. On the other hand, if the quenching temperature is too high, the old ⁇ grains are coarsened as described above, and the SSC resistance of the manufactured steel material is lowered.
- the upper limit of the more preferable quenching temperature is 995 ° C, more preferably 990 ° C.
- the lower limit of the more preferable quenching temperature is 880 ° C, more preferably 900 ° C.
- the quenching method is, for example, to continuously cool the intermediate steel material (raw pipe) from the quenching start temperature and continuously lower the surface temperature of the raw pipe.
- the method of continuous cooling treatment is not particularly limited, and a well-known method may be used.
- the method of continuous cooling treatment is, for example, a method of immersing the raw pipe in a water tank for cooling, or a method of accelerating cooling of the raw pipe by shower water cooling or mist cooling.
- the microstructure will not be mainly composed of martensite and bainite, and the mechanical properties specified in this embodiment cannot be obtained. In this case, further, excellent low temperature toughness and excellent SSC resistance cannot be obtained.
- the intermediate steel material is rapidly cooled at the time of quenching.
- the average cooling rate in the range where the surface temperature of the intermediate steel material (bare pipe) at the time of quenching is in the range of 800 to 500 ° C. is defined as the cooling rate at the time of quenching CR 800-500 .
- the quenching cooling rate CR 800-500 is the slowest cooling site in the cross section of the intermediate steel to be hardened (for example, the center of the intermediate steel thickness when both surfaces are forcibly cooled). Determined from the temperature measured in.
- the preferred quenching cooling rate CR 800-500 is at least 300 ° C./min.
- the lower limit of the more preferable quenching cooling rate CR 800-500 is 450 ° C./min, and more preferably 600 ° C./min.
- the upper limit of the cooling rate CR 800-500 during quenching is not particularly specified, but is, for example, 60,000 ° C./min.
- the raw tube is heated in the austenite region multiple times and then quenched.
- the SSC resistance of the steel material is enhanced.
- heating in the austenite region may be repeated a plurality of times, or by performing normalizing and quenching, heating in the austenite region may be repeated a plurality of times.
- quenching and tempering which will be described later, may be combined and carried out a plurality of times. That is, quenching and tempering may be carried out a plurality of times. In this case, the SSC resistance of the steel material is further enhanced.
- the tempering process will be described in detail.
- tempering means that the intermediate steel material after quenching is reheated at 1 point or less of Ac and held.
- the tempering temperature is appropriately adjusted according to the chemical composition of the steel material and the yield strength to be obtained. That is, the tempering temperature of the intermediate steel material (raw pipe) having the chemical composition of the present embodiment is adjusted to adjust the yield strength of the steel material to, for example, 758 MPa or more (110 ksi or more).
- the tempering temperature corresponds to the temperature of the furnace when the intermediate steel material after quenching is heated and held.
- the tempering time means the time from when the temperature of the intermediate steel material reaches a predetermined tempering temperature to when it is extracted from the heat treatment furnace.
- the dislocation density is reduced by raising the tempering temperature to as high as 600 to 730 ° C in order to improve SSC resistance.
- the alloy carbides are finely dispersed in the maintenance of tempering. Finely dispersed alloy carbides hinder the movement of dislocations and thus suppress the recovery of dislocations (that is, the disappearance of dislocations). Therefore, the dislocation density may not be sufficiently reduced only by tempering at a high temperature, which has been carried out to reduce the dislocation density.
- the steel material according to the present embodiment is tempered at a low temperature to reduce the dislocation density to some extent in advance. Further, tempering at a high temperature is performed to further reduce the dislocation density. That is, in the tempering step according to the present embodiment, tempering is carried out in two stages in the order of low temperature tempering and high temperature tempering. According to this method, the dislocation density can be reduced while maintaining the yield strength. In short, by performing two-step tempering, the dislocation density ⁇ and the yield strength ⁇ YS can satisfy the equation (2).
- the low-temperature tempering process and the high-temperature tempering process will be described in detail.
- the preferred tempering temperature in the low temperature tempering step is 100 to 550 ° C. If the tempering temperature in the low-temperature tempering step is too high, the alloy carbides may be finely dispersed during the holding of tempering, the dislocation density ⁇ may not be sufficiently reduced, and the SSC resistance of the steel material may be lowered. On the other hand, if the tempering temperature in the low-temperature tempering step is too low, the dislocation density ⁇ cannot be reduced during the holding of tempering, and the SSC resistance of the steel material may decrease. Therefore, the tempering temperature in the low temperature tempering step is preferably 100 to 550 ° C. A more preferable lower limit of the tempering temperature in the low temperature tempering step is 200 ° C. A more preferable upper limit of the tempering temperature in the low temperature tempering step is 500 ° C.
- the preferred tempering retention time (tempering time) in the low temperature tempering step is 10 to 90 minutes. If the tempering time in the low-temperature tempering step is too short, the dislocation density cannot be sufficiently reduced, and the SSC resistance of the steel material may decrease. On the other hand, if the tempering time in the low temperature tempering step is too long, the above effect is saturated. Therefore, in the present embodiment, the tempering time is preferably 10 to 90 minutes. A more preferable upper limit of the tempering time is 80 minutes. When the steel material is a steel pipe, the temperature variation of the steel pipe is likely to occur during the soaking heat retention of tempering as compared with other shapes. Therefore, when the steel material is a steel pipe, the tempering time is preferably 15 to 90 minutes.
- the dislocation density ⁇ is further reduced by performing tempering at a higher temperature than in the low temperature tempering step.
- the intermediate steel material in the high temperature tempering process if the old ⁇ grains are too coarse, the dislocation density ⁇ may not be sufficiently reduced.
- the coalescence of dislocation pairs with different signs and the dislocations are absorbed into the large-angle grain boundaries (boundaries with an orientation difference of 15 ° or more) corresponding to the block boundaries of rasmartensite. It is believed that it often occurs in.
- the block diameter also increases and the length of the dislocation line also increases.
- the alloy carbides are finely dispersed when the material is held at a high temperature.
- the length of the dislocation line becomes long, more contact is made with the alloy carbides that become obstacles when the dislocations move. Therefore, dislocations are difficult to move. As a result, it is considered that the coalescence of dislocation pairs having different signs and absorption into the large-angle grain boundaries are suppressed, and the recovery of dislocations is suppressed.
- the preferred tempering temperature in the high temperature tempering step is 580 to 740 ° C. If the tempering temperature in the high-temperature tempering step is too high, the dislocation density may be reduced too much and the desired yield strength may not be obtained. If the tempering temperature in the high-temperature tempering step is too high, austenite may be further generated in the microstructure, and a microstructure mainly composed of martensite and bainite may not be obtained. In this case, the SSC resistance of the steel material cannot be obtained. On the other hand, if the tempering temperature in the high-temperature tempering step is too low, the dislocation density cannot be sufficiently reduced, and the SSC resistance of the steel material may decrease.
- the preferred tempering temperature in the high temperature tempering step is 580 to 740 ° C.
- the lower limit of the more preferable tempering temperature in the high temperature tempering step is 600 ° C., and more preferably 610 ° C.
- the upper limit of the more preferable tempering temperature is 730 ° C, more preferably 720 ° C.
- the preferred tempering time in the high temperature tempering step is 10 to 180 minutes. If the tempering time is too short, the dislocation density cannot be sufficiently reduced, and the SSC resistance of the steel material may decrease. On the other hand, if the tempering time is too long, the above effect is saturated. Therefore, in this embodiment, the preferred tempering time is 10 to 180 minutes. A more preferable upper limit of the tempering time is 120 minutes, and even more preferably 90 minutes. When the steel material is a steel pipe, temperature variation is likely to occur as described above. Therefore, when the steel material is a steel pipe, the tempering time is preferably 15 to 180 minutes.
- the above-mentioned low-temperature tempering step and high-temperature tempering step can be carried out as continuous heat treatment. That is, in the low-temperature tempering step, the high-temperature tempering step may be carried out by carrying out the above-mentioned tempering holding and then heating. At this time, the low temperature tempering step and the high temperature tempering step may be carried out in the same heat treatment furnace.
- the above-mentioned low-temperature tempering step and high-temperature tempering step can also be carried out as discontinuous heat treatment. That is, in the low-temperature tempering step, the above-mentioned tempering may be maintained, then cooled to a temperature lower than the above-mentioned tempering temperature, and then heated again to carry out the high-temperature tempering step. Even in this case, the effects obtained in the low-temperature tempering step and the high-temperature tempering step are not impaired, and the steel material according to the present embodiment can be manufactured.
- the steel material according to the present embodiment can be manufactured.
- a method for manufacturing a steel pipe has been described as an example.
- the steel material according to this embodiment may be a steel plate or another shape.
- a method for manufacturing a steel sheet or another shape also includes, for example, a preparation step, a quenching step, and a tempering step.
- the above-mentioned manufacturing method is an example, and may be manufactured by another manufacturing method.
- Example 1 a steel material having a yield strength of 110 ksi class (758 to less than 862 MPa) was investigated. Specifically, 180 kg of molten steel having the chemical composition shown in Table 1 was produced. In addition, "-" in Table 1 means that the content of the corresponding element was the impurity level. Further, Table 1 shows the chemical composition shown in Table 1 and Fn1 obtained from the above definition.
- FIG. 3 is a side view of the test piece used when determining the A c3 point in this embodiment.
- the L direction in FIG. 3 corresponds to the plate thickness direction of the steel plates of test numbers 1-1 to 1-30.
- thermocouple was welded to the points P of the test pieces of test numbers 1-1 to 1-30, and heated from room temperature to 1250 ° C. at a heating rate of 20 ° C./min.
- the length of the test piece of each test number in the L direction during heating was measured, and the relationship between the coefficient of thermal expansion and the temperature was plotted. From the resulting plots, the temperature range of the austenite single phase was identified. The lowest temperature in the identified austenite single-phase temperature range was defined as the Ac3 point.
- the steel sheets of test numbers 1-1 to 1-30 were heated to the quenching temperature (° C.) shown in Table 2.
- the quenching temperature of test numbers 1-1 to 1-30 was set to A c3 points or more on the steel sheets of each test number obtained by the above method.
- the steel sheets of test numbers 1-1 to 1-30 were held at the quenching temperature for 20 minutes, and then water-cooled using a shower-type water-cooling device.
- the quenching temperature and the cooling rate at the time of quenching were measured by a sheath-type K thermocouple previously charged in the central portion of the thickness of the steel sheet.
- the hardened steel sheets of test numbers 1-1 to 1-30 were further quenched under the same conditions for the second time.
- the average cooling rate between 800 ° C and 500 ° C at the time of quenching that is, the cooling rate at the time of quenching (CR 800-500 ) (° C / sec) is 10 ° C / sec. Met.
- tempering was performed on the steel sheets of test numbers 1-1 to 1-30.
- the first tempering and the second tempering were performed on the steel sheets of test numbers 1-1 to 1-14 and 1-16 to 1-30.
- the steel sheet of test number 1-15 was tempered only once.
- Table 2 shows the tempering temperature (° C.) and the tempering time (minutes) for each of the first tempering and the second tempering.
- the tempering temperature was the temperature of the furnace in which the tempering was performed.
- the tempering time was defined as the time after the temperature of the steel sheet of each test number reached a predetermined tempering temperature until it was extracted from the furnace.
- Test test Tensile tests were carried out on the steel sheets of test numbers 1-1 to 1-30. Tensile tests were performed in accordance with ASTM E8 / E8M (2013). A round bar test piece having a parallel portion diameter of 4 mm and a gauge point distance of 20 mm was prepared from the central portion of the plate thickness of the steel plates of test numbers 1-1 to 1-30. The axial direction of the round bar test piece was parallel to the rolling direction of the steel sheet. Tensile tests were carried out in the air at room temperature (25 ° C.) using the prepared round bar test pieces to obtain yield strength ⁇ YS (MPa) of the steel sheets of test numbers 1-1 to 1-30.
- the 0.2% offset proof stress obtained in the tensile test was defined as the yield strength ⁇ YS .
- the obtained yield strength ⁇ YS is shown in Table 2 as “ ⁇ YS (MPa)”.
- Dislocation density measurement test A dislocation density measurement test was carried out on the steel sheets of test numbers 1-1 to 1-30. Specifically, a test piece for measuring the dislocation density was prepared from the steel sheets of test numbers 1-1 to 1-30 by the above method. Further, the dislocation density ⁇ (m -2 ) was determined by the above-mentioned method using the test pieces of test numbers 1-1 to 1-30. The dislocation density ⁇ obtained for the steel sheets of test numbers 1-1 to 1-30 is shown in Table 2 as "dislocation density ⁇ (10 14 m -2 )". Table 2 shows the dislocation density ⁇ obtained, the yield strength ⁇ YS obtained, and Fn2 obtained from the above definitions for the steel sheets of test numbers 1-1 to 1-30.
- SSC resistance evaluation test An SSC resistance evaluation test was carried out on the steel sheets of test numbers 1-1 to 1-30. SSC resistance was evaluated by a method compliant with NACE TM0177-2005 Method A. Specifically, a round bar test piece having a diameter of 6.35 mm and a parallel portion having a length of 25.4 mm was produced from the central portion of the plate thickness of the steel plates of test numbers 1-1 to 1-30. A room temperature SSC resistance test was carried out on three of the prepared test pieces. A low temperature SSC resistance test was carried out on the other three of the prepared test pieces. The axial direction of the test piece was parallel to the rolling direction.
- the room temperature SSC resistance test was carried out as follows. Tensile stress was applied in the axial direction of the round bar test pieces of test numbers 1-1 to 1-30. At this time, the stress applied was adjusted to be 95% of the actual yield stress of each steel sheet.
- As the test solution a mixed aqueous solution (NACE solution A) of 5.0% by mass sodium chloride and 0.5% by mass acetic acid was used.
- a test solution at 24 ° C. was poured into each of the three test containers to prepare a test bath. The three stressed round bar test pieces were immersed in the test baths of different test containers one by one. After degassing each test bath, 1 atm of H2S gas was blown into the test bath to saturate it. A test bath saturated with 1 atm of H2S gas was kept at 24 ° C. for 720 hours.
- SSC sulfide stress cracking
- the low temperature SSC resistance test was carried out in accordance with NACE TM0177-2005 Method A, as in the normal temperature SSC resistance test.
- the applied stress was adjusted to be 90% of the actual yield stress of each steel sheet.
- NACE solution A was used as in the room temperature SSC resistance test. Further, the temperature of the test bath was set to 4 ° C. Other conditions were the same as in the room temperature SSC resistance test.
- SSC sulfide stress cracking
- the steel sheet of test number 1-15 was not tempered at low temperature. As a result, Fn2 was 691 or less. As a result, the steel sheet of Test No. 1-15 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the steel sheet of test number 1-16 was tempered at a low temperature after being tempered at a high temperature. As a result, Fn2 was 691 or less. As a result, the steel sheet of Test No. 1-16 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the Si content of the steel sheets of test numbers 1-17 and 1-18 was too low. As a result, Fn2 was 691 or less. As a result, the steel sheets of test numbers 1-17 and 1-18 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the steel sheet of test number 1-19 had a Cr content that was too low. As a result, the steel sheet of Test No. 1-19 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the Mo content of the steel sheet of test number 1-20 was too low. As a result, Fn2 was 691 or less. As a result, the steel sheet of Test No. 1-20 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the steel sheet of test number 1-21 had too high Mn content. As a result, the steel sheet of Test No. 1-21 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the N content of the steel sheet of test number 1-22 was too high. As a result, the steel sheet of Test No. 1-22 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the P content of the steel sheet of test number 1-23 was too high. As a result, the steel sheet of Test No. 1-23 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the V content of the steel sheet of test number 1-24 was too low. As a result, Fn2 was 691 or less. As a result, the steel sheet of Test No. 1-24 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the steel plates of test numbers 1-25 and 1-26 had Fn1 of 85 or less. As a result, Fn2 was 691 or less. As a result, the steel sheets of test numbers 1-25 and 1-26 did not show excellent SSC resistance in either the normal temperature SSC resistance test or the low temperature SSC resistance test.
- the Mo content of the steel sheet of test number 1-27 was too low. As a result, the steel sheet of Test No. 1-27 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the steel sheet of test number 1-28 had too high Mn content. As a result, the steel sheet of Test No. 1-28 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the steel sheet of test number 1-29 had too high Ti content. As a result, the steel sheet of Test No. 1-29 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the Nb content of the steel sheet of test number 1-30 was too high. As a result, the steel sheet of Test No. 1-30 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- Example 2 a steel material having a yield strength of 125 ksi class (862 to less than 965 MPa) was investigated. Specifically, 180 kg of molten steel having the chemical composition shown in Table 3 was produced. In addition, "-" in Table 3 means that the content of the corresponding element was the impurity level. Further, Table 3 shows the chemical composition shown in Table 3 and Fn1 obtained from the above definition.
- Example 1 An ingot was manufactured using the above molten steel. The ingot was hot-rolled to produce a steel plate having a thickness of 15 mm. After hot rolling, the steel sheets of test numbers 2-1 to 2-30 whose temperature was set to room temperature were quenched twice. First, the A c3 points of the steel sheets of test numbers 2-1 to 2-30 were obtained by the same method as in Example 1. That is, as in Example 1, the lowest temperature in the austenite single-phase temperature range identified from the relationship between the coefficient of thermal expansion and the temperature of the test piece was defined as the A c3 point.
- the steel sheets of test numbers 2-1 to 2-30 were heated to the quenching temperature (° C.) shown in Table 4.
- the quenching temperature of test numbers 2-1 to 2-30 was set to A c3 points or more on the steel sheets of each test number obtained by the above method.
- the steel sheets of test numbers 2-1 to 2-30 were held at the quenching temperature for 20 minutes, and then water-cooled using a shower-type water-cooling device.
- the quenching temperature and the cooling rate at the time of quenching were measured by a sheath-type K thermocouple previously charged in the central portion of the thickness of the steel sheet.
- the hardened steel sheets of test numbers 2-1 to 2-30 were further quenched under the same conditions for the second time.
- the average cooling rate between 800 ° C and 500 ° C at the time of quenching that is, the cooling rate at the time of quenching (CR 800-500 ) (° C / sec) is 10 ° C / sec. Met.
- tempering was performed on the steel sheets of test numbers 2-1 to 2-30.
- the first tempering and the second tempering were carried out.
- the steel sheet of test number 2-15 was tempered only once.
- Table 4 shows the tempering temperature (° C.) and the tempering time (minutes) for each of the first tempering and the second tempering.
- the tempering temperature was the temperature of the furnace in which the tempering was performed.
- the tempering time was defined as the time after the temperature of the steel sheet of each test number reached a predetermined tempering temperature until it was extracted from the furnace.
- Test test A tensile test was carried out on the steel sheets of test numbers 2-1 to 2-30 by the same method as in Example 1. Specifically, a round bar test piece having a parallel portion diameter of 4 mm, a gauge point distance of 20 mm, and an axial direction parallel to the rolling direction of the steel plate from the central portion of the plate thickness of the steel plates of test numbers 2-1 to 2-30. was produced. Using the prepared round bar test piece, a tensile test conforming to ASTM E8 / E8M (2013) was carried out at room temperature (25 ° C) in the air, and the yield of the steel sheet of test numbers 2-1 to 2-30 was yielded. The intensity ⁇ YS (MPa) was obtained.
- the 0.2% offset proof stress obtained in the tensile test was defined as the yield strength ⁇ YS .
- the obtained yield strength ⁇ YS is shown in Table 4 as “ ⁇ YS (MPa)”.
- Dislocation density measurement test A dislocation density measurement test was carried out on the steel sheets of test numbers 2-1 to 2-30. Specifically, a test piece for measuring the dislocation density was prepared from the steel sheets of test numbers 2-1 to 2-30 by the above-mentioned method. Further, the dislocation density ⁇ (m -2 ) was determined by the above-mentioned method using the test pieces of test numbers 2-1 to 2-30. The dislocation density ⁇ obtained for the steel sheets of test numbers 2-1 to 2-30 is shown in Table 4 as "dislocation density ⁇ (10 14 m -2 )". Table 4 shows the dislocation density ⁇ obtained, the yield strength ⁇ YS obtained, and Fn2 obtained from the above definitions for the steel sheets of test numbers 2-1 to 2-30.
- the old ⁇ grain size measurement test was carried out on the steel sheets of test numbers 2-1 to 2-30. Specifically, a test piece for measuring the old ⁇ particle size was prepared from the steel plates of test numbers 2-1 to 2-30 by the above method. Further, the old ⁇ particle size ( ⁇ m) was determined by the above-mentioned method using the test pieces of test numbers 2-1 to 2-30. The old ⁇ grain size obtained for the steel sheets of test numbers 2-1 to 2-30 is shown in Table 4 as “old ⁇ grain size ( ⁇ m)”.
- SSC resistance evaluation test An SSC resistance evaluation test was carried out on the steel sheets of test numbers 2-1 to 2-30. SSC resistance was evaluated by a method compliant with NACE TM0177-2005 Method A. Specifically, a round bar test piece having a diameter of 6.35 mm and a parallel portion having a length of 25.4 mm was produced from the central portion of the plate thickness of the steel plates of test numbers 2-1 to 2-30. A room temperature SSC resistance test was carried out on three of the prepared test pieces. A low temperature SSC resistance test was carried out on the other three of the prepared test pieces. The axial direction of the test piece was parallel to the rolling direction.
- the room temperature SSC resistance test was carried out as follows. Tensile stress was applied in the axial direction of the round bar test pieces of test numbers 2-1 to 2-30. At this time, the stress applied was adjusted to be 95% of the actual yield stress of each steel sheet.
- As the test solution a mixed aqueous solution (NACE solution A) of 5.0% by mass sodium chloride and 0.5% by mass acetic acid was used.
- a test solution at 24 ° C. was poured into each of the three test containers to prepare a test bath. The three stressed round bar test pieces were immersed in the test baths of different test containers one by one. After degassing each test bath, 1 atm of H2S gas was blown into the test bath to saturate it. A test bath saturated with 1 atm of H2S gas was held at 24 ° C. for 720 hours.
- SSC sulfide stress cracking
- the low temperature SSC resistance test was carried out in accordance with NACE TM0177-2005 Method A, as in the normal temperature SSC resistance test.
- the applied stress was adjusted to be 85% of the actual yield stress of each steel sheet.
- NACE solution A was used as in the room temperature SSC resistance test. Further, the temperature of the test bath was set to 4 ° C. Other conditions were the same as in the room temperature SSC resistance test.
- SSC sulfide stress cracking
- the chemical composition of the steel sheets of test numbers 2-1 to 2-14 was appropriate, and Fn1 exceeded 85. Furthermore, Fn2 exceeded 691. As a result, the steel sheets of test numbers 2-1 to 2-14 showed excellent SSC resistance in the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the steel sheet of test number 2-15 was not tempered at low temperature. As a result, Fn2 was 691 or less. As a result, the steel sheet of Test No. 2-15 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the steel sheet of test number 2-16 was tempered at a low temperature after being tempered at a high temperature. As a result, Fn2 was 691 or less. As a result, the steel sheet of Test No. 2-16 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the Si content of the steel sheet of test number 2-17 was too low. As a result, Fn2 was 691 or less. As a result, the steel sheet of Test No. 2-17 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the steel sheet of test number 2-18 had a Cr content that was too low. As a result, the steel sheet of Test No. 2-18 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the Mo content of the steel sheet of test number 2-19 was too low. As a result, Fn2 was 691 or less. As a result, the steel sheet of Test No. 2-19 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the steel sheet of test number 2-20 had too high Mn content. As a result, the steel sheet of Test No. 2-20 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the N content of the steel sheet of test number 2-21 was too high. As a result, the steel sheet of Test No. 2-21 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the P content of the steel sheet of test number 2-22 was too high. As a result, the steel sheet of Test No. 2-22 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the Si content of the steel sheet of test number 2-23 was too low. As a result, Fn2 was 691 or less. As a result, the steel sheet of test number 2-23 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the steel plates of test numbers 2-24 and 2-25 had Fn1 of 85 or less. As a result, Fn2 was 691 or less. As a result, the steel sheets of test numbers 2-24 and 2-25 did not show excellent SSC resistance in either the normal temperature SSC resistance test or the low temperature SSC resistance test.
- the V content of the steel sheet of test number 2-26 was too low. As a result, Fn2 was 691 or less. As a result, the steel sheet of Test No. 2-26 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the Mo content of the steel sheet of test number 2-27 was too low. As a result, the steel sheet of Test No. 2-27 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the steel sheet of test number 2-28 had too high Mn content. As a result, the steel sheet of Test No. 2-28 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the steel sheet of test number 2-29 had too high Ti content. As a result, the steel sheet of Test No. 2-29 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the Nb content of the steel sheet of test number 2-30 was too high. As a result, the steel sheet of Test No. 2-30 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- Example 3 a steel material having a yield strength of 140 ksi or more (965 MPa or more) was investigated. Specifically, 180 kg of molten steel having the chemical composition shown in Table 5 was produced. In addition, "-" in Table 5 means that the content of the corresponding element was the impurity level. Further, Table 5 shows the chemical composition shown in Table 5 and Fn1 obtained from the above definition.
- Example 1 An ingot was manufactured using the above molten steel. The ingot was hot-rolled to produce a steel plate having a thickness of 15 mm. After hot rolling, the steel sheets of test numbers 3-1 to 3-30 at room temperature were hardened twice. First, the A c3 points of the steel sheets of test numbers 3-1 to 3-30 were obtained by the same method as in Example 1. That is, as in Example 1, the lowest temperature in the austenite single-phase temperature range identified from the relationship between the coefficient of thermal expansion and the temperature of the test piece was defined as the A c3 point.
- the quenching temperature of test numbers 3-1 to 3-30 was set to A c3 points or more on the steel sheets of each test number obtained by the above method.
- the steel sheets of test numbers 3-1 to 3-30 were held at the quenching temperature for 20 minutes, and then water-cooled using a shower-type water-cooling device.
- the quenching temperature and the cooling rate at the time of quenching were measured by a sheath-type K thermocouple previously charged in the central portion of the thickness of the steel sheet.
- the hardened steel sheets of test numbers 3-1 to 3-30 were further quenched under the same conditions for the second time.
- the average cooling rate between 800 ° C and 500 ° C at the time of quenching that is, the cooling rate at the time of quenching (CR 800-500 ) (° C / sec) is 10 ° C / sec. Met.
- tempering was performed on the steel sheets of test numbers 3-1 to 3-30.
- the first tempering and the second tempering were carried out for the steel sheets of test numbers 3-1 to 3-14 and 3-16 to 3-30.
- the steel sheet of test number 3-15 was tempered only once.
- Table 6 shows the tempering temperature (° C.) and the tempering time (minutes) for each of the first tempering and the second tempering.
- the tempering temperature was the temperature of the furnace in which the tempering was performed.
- the tempering time was defined as the time after the temperature of the steel sheet of each test number reached a predetermined tempering temperature until it was extracted from the furnace.
- Test test A tensile test was carried out on the steel sheets of test numbers 3-1 to 3-30 by the same method as in Example 1. Specifically, a round bar test piece having a parallel portion diameter of 4 mm, a gauge point distance of 20 mm, and an axial direction parallel to the rolling direction of the steel plate from the central portion of the thickness of the steel plate of test numbers 3-1 to 3-30. was produced. Using the prepared round bar test piece, a tensile test conforming to ASTM E8 / E8M (2013) was carried out at room temperature (25 ° C) in the air, and the yield of the steel sheet of test numbers 3-1 to 3-30 was yielded. The intensity ⁇ YS (MPa) was obtained.
- the 0.2% offset proof stress obtained in the tensile test was defined as the yield strength ⁇ YS .
- the obtained yield strength ⁇ YS is shown in Table 6 as “ ⁇ YS (MPa)”.
- Dislocation density measurement test A dislocation density measurement test was carried out on the steel sheets of test numbers 3-1 to 3-30. Specifically, a test piece for measuring the dislocation density was prepared from the steel sheets of test numbers 3-1 to 3-30 by the above-mentioned method. Further, the dislocation density ⁇ (m -2 ) was determined by the above-mentioned method using the test pieces of test numbers 3-1 to 3-30. The dislocation density ⁇ obtained for the steel sheets of test numbers 3-1 to 3-30 is shown in Table 6 as "dislocation density ⁇ (10 14 m -2 )". Table 6 shows the dislocation density ⁇ obtained, the yield strength ⁇ YS obtained, and Fn2 obtained from the above definitions for the steel sheets of test numbers 3-1 to 3-30.
- the old ⁇ grain size measurement test was carried out on the steel sheets of test numbers 3-1 to 3-30. Specifically, a test piece for measuring the old ⁇ particle size was prepared from the steel plates of test numbers 3-1 to 3-30 by the above method. Further, the old ⁇ particle size ( ⁇ m) was determined by the above-mentioned method using the test pieces of test numbers 3-1 to 3-30. The old ⁇ grain size obtained for the steel sheets of test numbers 3-1 to 3-30 is shown in Table 6 as “old ⁇ grain size ( ⁇ m)”.
- SSC resistance evaluation test An SSC resistance evaluation test was carried out on the steel sheets of test numbers 3-1 to 3-30. SSC resistance was evaluated by a method compliant with NACE TM0177-2005 Method A. Specifically, a round bar test piece having a diameter of 6.35 mm and a parallel portion having a length of 25.4 mm was produced from the central portion of the plate thickness of the steel plates of test numbers 3-1 to 3-30. A room temperature SSC resistance test was carried out on three of the prepared test pieces. A low temperature SSC resistance test was carried out on the other three of the prepared test pieces. The axial direction of the test piece was parallel to the rolling direction.
- the room temperature SSC resistance test was carried out as follows. Tensile stress was applied in the axial direction of the round bar test pieces of test numbers 3-1 to 3-30. At this time, the stress applied was adjusted to be 95% of the actual yield stress of each steel sheet.
- As the test solution a mixed aqueous solution (NACE solution B) of 5.0% by mass sodium chloride and 0.4% by mass sodium acetate adjusted to pH 3.5 with acetic acid was used.
- a test solution at 24 ° C. was poured into each of the three test containers to prepare a test bath. The three stressed round bar test pieces were immersed in the test baths of different test containers one by one.
- SSC sulfide stress cracking
- the low temperature SSC resistance test was carried out in accordance with NACE TM0177-2005 Method A, as in the normal temperature SSC resistance test.
- the applied stress was adjusted to be 85% (820 MPa) of 965 MPa.
- NACE solution B was used as in the room temperature SSC resistance test. Further, the temperature of the test bath was set to 4 ° C. Other conditions were the same as in the room temperature SSC resistance test.
- SSC sulfide stress cracking
- the steel sheet of test number 3-15 was not tempered at low temperature. As a result, Fn2 was 691 or less. As a result, the steel sheet of Test No. 3-15 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the steel sheet of test number 3-16 was tempered at a low temperature after being tempered at a high temperature. As a result, Fn2 was 691 or less. As a result, the steel sheet of test number 3-16 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the Si content of the steel sheet of test number 3-17 was too low. As a result, Fn2 was 691 or less. As a result, the steel sheet of test number 3-17 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the steel sheet of test number 3-18 had a Cr content that was too low. As a result, the steel sheet of Test No. 3-18 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the Mo content of the steel sheet of test number 3-19 was too low. As a result, Fn2 was 691 or less. As a result, the steel sheet of Test No. 3-19 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the steel sheet of test number 3-20 had too high Mn content. As a result, the steel sheet of Test No. 3-20 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the N content of the steel sheet of test number 3-21 was too high. As a result, the steel sheet of Test No. 3-21 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the P content of the steel sheet of test number 3-22 was too high. As a result, the steel sheet of Test No. 3-22 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the Si content of the steel sheet of test number 3-23 was too low. As a result, Fn2 was 691 or less. As a result, the steel sheet of test number 3-23 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the steel plates of test numbers 3-24 and 3-25 had Fn1 of 85 or less. As a result, Fn2 was 691 or less. As a result, the steel sheets of test numbers 3-24 and 3-25 did not show excellent SSC resistance in either the normal temperature SSC resistance test or the low temperature SSC resistance test.
- the V content of the steel sheet of test number 3-26 was too low. As a result, Fn2 was 691 or less. As a result, the steel sheet of Test No. 3-26 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the Mo content of the steel sheet of test number 3-27 was too low. As a result, the steel sheet of Test No. 3-27 did not show excellent SSC resistance in the low temperature SSC resistance test.
- the steel sheet of test number 3-28 had too high Mn content. As a result, the steel sheet of Test No. 3-28 did not show excellent SSC resistance in either the normal temperature SSC resistance test or the low temperature SSC resistance test.
- the steel sheet of test number 3-29 had too high Ti content. As a result, the steel sheet of Test No. 3-29 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
- the Nb content of the steel sheet of test number 3-30 was too high. As a result, the steel sheet of Test No. 3-30 did not show excellent SSC resistance in both the normal temperature SSC resistance test and the low temperature SSC resistance test.
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Abstract
Description
質量%で、
C:0.20~0.45%、
Si:1.36~3.20%、
Mn:0.02~1.00%、
P:0.025%以下、
S:0.0100%以下、
Al:0.005~0.100%、
Cr:0.20~1.50%、
Mo:0.36~1.50%、
V:0.01~0.90%、
Ti:0.002~0.050%、
B:0.0001~0.0050%、
N:0.0100%以下、
O:0.0100%以下、
Nb:0~0.030%、
Ca:0~0.0100%、
Mg:0~0.0100%、
Zr:0~0.0100%、
希土類元素:0~0.0100%、
Co:0~0.50%、
W:0~0.50%、
Ni:0~0.50%、
Cu:0~0.50%、及び、
残部がFe及び不純物からなり、式(1)を満たし、
降伏強度σYSが758MPa以上であり、
降伏強度σYSと転位密度ρとが式(2)を満たす。
27×Mn+9×Cr-14×Mo-770×C2+760×C-11×Si2+4×Si>85 (1)
691<σYS-110×√ρ×10-7≦795 (2)
ここで、式(1)中の元素記号には、対応する元素の含有量が質量%で代入される。式(2)中のσYSには降伏強度がMPaで代入され、ρには転位密度がm-2で代入される。
691<σYS-110×√ρ×10-7≦795 (2)
ここで、式(2)中のσYSには降伏強度がMPaで代入され、ρには転位密度がm-2で代入される。
27×Mn+9×Cr-14×Mo-770×C2+760×C-11×Si2+4×Si>85 (1)
ここで、式(1)中の元素記号には、対応する元素の含有量が質量%で代入される。
質量%で、
C:0.20~0.45%、
Si:1.36~3.20%、
Mn:0.02~1.00%、
P:0.025%以下、
S:0.0100%以下、
Al:0.005~0.100%、
Cr:0.20~1.50%、
Mo:0.36~1.50%、
V:0.01~0.90%、
Ti:0.002~0.050%、
B:0.0001~0.0050%、
N:0.0100%以下、
O:0.0100%以下、
Nb:0~0.030%、
Ca:0~0.0100%、
Mg:0~0.0100%、
Zr:0~0.0100%、
希土類元素:0~0.0100%、
Co:0~0.50%、
W:0~0.50%、
Ni:0~0.50%、
Cu:0~0.50%、及び、
残部がFe及び不純物からなり、式(1)を満たし、
降伏強度σYSが758MPa以上であり、
降伏強度σYSと転位密度ρとが式(2)を満たす、
鋼材。
27×Mn+9×Cr-14×Mo-770×C2+760×C-11×Si2+4×Si>85 (1)
691<σYS-110×√ρ×10-7≦795 (2)
ここで、式(1)中の元素記号には、対応する元素の含有量が質量%で代入される。式(2)中のσYSには降伏強度がMPaで代入され、ρには転位密度がm-2で代入される。
[1]に記載の鋼材であって、
Nb:0.002~0.030%、
Ca:0.0001~0.0100%、
Mg:0.0001~0.0100%、
Zr:0.0001~0.0100%、
希土類元素:0.0001~0.0100%、
Co:0.02~0.50%、
W:0.02~0.50%、
Ni:0.01~0.50%、及び、
Cu:0.01~0.50%からなる群から選択される1元素以上を含有する、
鋼材。
[1]又は[2]に記載の鋼材であって、
前記鋼材は油井用鋼管である、
鋼材。
本実施形態による鋼材の化学組成は、次の元素を含有する。
炭素(C)は鋼材の焼入れ性を高め、鋼材の強度を高める。Cはさらに、製造工程中の焼戻しにおいて、炭化物の球状化を促進し、鋼材の耐SSC性を高める。炭化物が分散されればさらに、鋼材の強度が高まる。C含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、C含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、炭化物が多くなりすぎ、鋼材の靭性が低下する。C含有量が高すぎればさらに、製造工程中の焼入れにおいて、焼割れが発生しやすくなる場合がある。したがって、C含有量は0.20~0.45%である。C含有量の好ましい下限は0.22%であり、さらに好ましくは0.23%であり、さらに好ましくは0.24%であり、さらに好ましくは0.25%である。C含有量の好ましい上限は0.40%であり、さらに好ましくは0.38%であり、さらに好ましくは0.37%である。
ケイ素(Si)は鋼を脱酸する。Siはさらに、鋼材の転位密度を低減し、鋼材の耐SSC性を高める。Si含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、Si含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、鋼材の耐SSC性が低下する。したがって、Si含有量は1.36~3.20%である。Si含有量の好ましい下限は1.38%であり、さらに好ましくは1.40%であり、さらに好ましくは1.45%であり、さらに好ましくは1.50%であり、さらに好ましくは1.70%である。Si含有量の好ましい上限は3.10%であり、さらに好ましくは3.00%であり、さらに好ましくは2.90%である。
マンガン(Mn)は鋼を脱酸する。Mnはさらに、鋼材の焼入れ性を高める。Mn含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、Mn含有量が高すぎれば、Mnは、P及びS等の不純物とともに、結晶粒界に偏析する。その結果、他の元素含有量が本実施形態の範囲内であっても、鋼材の耐SSC性が低下する。したがって、Mn含有量は0.02~1.00%である。Mn含有量の好ましい下限は0.03%であり、さらに好ましくは0.05%であり、さらに好ましくは0.10%である。Mn含有量の好ましい上限は0.90%であり、さらに好ましくは0.80%であり、さらに好ましくは0.70%であり、さらに好ましくは0.65%である。
燐(P)は不純物である。すなわち、P含有量の下限は0%超である。P含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、Pが粒界に偏析し、鋼材の耐SSC性が低下する。したがって、P含有量は0.025%以下である。P含有量の好ましい上限は0.020%であり、さらに好ましくは0.015%である。P含有量はなるべく低い方が好ましい。ただし、P含有量の極端な低減は、製造コストを大幅に高める。したがって、工業生産を考慮した場合、P含有量の好ましい下限は0.0001%であり、さらに好ましくは0.0003%であり、さらに好ましくは0.001%であり、さらに好ましくは0.003%である。
硫黄(S)は不純物である。すなわち、S含有量の下限は0%超である。S含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、Sが粒界に偏析し、鋼材の耐SSC性が低下する。したがって、S含有量は0.0100%以下である。S含有量の好ましい上限は0.0050%であり、さらに好ましくは0.0030%である。S含有量はなるべく低い方が好ましい。ただし、S含有量の極端な低減は、製造コストを大幅に高める。したがって、工業生産を考慮した場合、S含有量の好ましい下限は0.0001%であり、さらに好ましくは0.0002%であり、さらに好ましくは0.0003%である。
アルミニウム(Al)は鋼を脱酸する。Al含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られず、鋼材の耐SSC性が低下する。一方、Al含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、粗大な酸化物系介在物が生成して、鋼材の耐SSC性が低下する。したがって、Al含有量は0.005~0.100%である。Al含有量の好ましい下限は0.015%であり、さらに好ましくは0.020%である。Al含有量の好ましい上限は0.080%であり、さらに好ましくは0.060%である。本明細書にいう「Al」含有量は「酸可溶Al」、つまり、「sol.Al」の含有量を意味する。
クロム(Cr)は鋼材の焼入れ性を高める。Crはさらに、鋼材の焼戻し軟化抵抗を高め、高温焼戻しを可能にする。その結果、鋼材の耐SSC性が高まる。Cr含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、Cr含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、鋼材の耐SSC性が低下する。したがって、Cr含有量は0.20~1.50%である。Cr含有量の好ましい下限は0.25%であり、さらに好ましくは0.30%であり、さらに好ましくは0.35%であり、さらに好ましくは0.40%である。Cr含有量の好ましい上限は1.40%であり、さらに好ましくは1.30%である。
モリブデン(Mo)は鋼材の焼入れ性を高める。Moはさらに、鋼材の焼戻し軟化抵抗を高め、高温焼戻しを可能にする。その結果、鋼材の耐SSC性が高まる。Mo含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、Mo含有量が高すぎれば、上記効果が飽和する。したがって、Mo含有量は0.36~1.50%である。Mo含有量の好ましい下限は0.40%であり、さらに好ましくは0.50%であり、さらに好ましくは0.60%である。Mo含有量の好ましい上限は1.40%であり、さらに好ましくは1.30%であり、さらに好ましくは1.25%である。
バナジウム(V)はC及び/又はNと結合して、炭化物、窒化物又は炭窒化物(以下、「炭窒化物等」という)を形成する。炭窒化物等は、ピンニング効果により鋼材のサブ組織を微細化し、鋼材の耐SSC性を高める。Vはさらに、焼戻し軟化抵抗を高め、高温焼戻しを可能にする。その結果、鋼材の耐SSC性が高まる。V含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、V含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、鋼材の靭性が低下する。したがって、V含有量は0.01~0.90%である。V含有量の好ましい下限は0.02%であり、さらに好ましくは0.04%であり、さらに好ましくは0.06%であり、さらに好ましくは0.08%である。V含有量の好ましい上限は0.85%であり、さらに好ましくは0.80%であり、さらに好ましくは0.75%であり、さらに好ましくは0.70%であり、さらに好ましくは0.60%であり、さらに好ましくは0.50%である。
チタン(Ti)はNと結合して窒化物を形成し、ピンニング効果により、鋼材の結晶粒を微細化する。その結果、鋼材の強度が高まる。Ti含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、Ti含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、Ti窒化物が粗大化して、鋼材の耐SSC性が低下する。したがって、Ti含有量は0.002~0.050%である。Ti含有量の好ましい下限は0.003%であり、さらに好ましくは0.005%である。Ti含有量の好ましい上限は0.040%であり、さらに好ましくは0.030%であり、さらに好ましくは0.020%である。
ホウ素(B)は鋼に固溶して鋼材の焼入れ性を高め、鋼材の強度を高める。B含有量が低すぎれば、他の元素含有量が本実施形態の範囲内であっても、上記効果が十分に得られない。一方、B含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、粗大な窒化物が生成して、鋼材の耐SSC性が低下する。したがって、B含有量は0.0001~0.0050%である。B含有量の好ましい下限は0.0003%であり、さらに好ましくは0.0007%である。B含有量の好ましい上限は0.0030%であり、さらに好ましくは0.0025%であり、さらに好ましくは0.0020%であり、さらに好ましくは0.0015%である。
窒素(N)は不可避に含有される。すなわち、N含有量の下限は0%超である。NはTiと結合して窒化物を形成し、ピンニング効果により、鋼材の結晶粒を微細化する。その結果、鋼材の強度が高まる。しかしながら、N含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、粗大な窒化物が形成され、鋼材の耐SSC性が低下する。したがって、N含有量は0.0100%以下である。N含有量の好ましい上限は0.0050%であり、さらに好ましくは0.0045%である。上記効果をより有効に得るためのN含有量の好ましい下限は0.0005%であり、さらに好ましくは0.0010%であり、さらに好ましくは0.0015%であり、さらに好ましくは0.0020%である。
酸素(O)は不純物である。すなわち、O含有量の下限は0%超である。O含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、粗大な酸化物が形成し、鋼材の低温靭性及び耐SSC性が低下する。したがって、O含有量は0.0100%以下である。O含有量の好ましい上限は0.0050%であり、さらに好ましくは0.0030%であり、さらに好ましくは0.0020%である。O含有量はなるべく低い方が好ましい。ただし、O含有量の極端な低減は、製造コストを大幅に高める。したがって、工業生産を考慮した場合、O含有量の好ましい下限は0.0001%であり、さらに好ましくは0.0002%であり、さらに好ましくは0.0003%である。
上述の鋼材の化学組成はさらに、Feの一部に代えて、Nbを含有してもよい。
ニオブ(Nb)は任意元素であり、含有されなくてもよい。すなわち、Nb含有量は0%であってもよい。含有される場合、Nbは炭窒化物等を形成する。炭窒化物等はピンニング効果により、鋼材の結晶粒を微細化し、鋼材の低温靭性及び耐SSC性を高める。Nbはさらに、焼戻し時に微細な炭化物を形成して鋼材の焼戻し軟化抵抗を高め、鋼材の強度を高める。Nbが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Nb含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、炭窒化物等が過剰に生成して、鋼材の耐SSC性が低下する。したがって、Nb含有量は0~0.030%である。Nb含有量の好ましい下限は0%超であり、さらに好ましくは0.002%であり、さらに好ましくは0.003%であり、さらに好ましくは0.007%である。Nb含有量の好ましい上限は0.025%であり、さらに好ましくは0.020%である。
カルシウム(Ca)は任意元素であり、含有されなくてもよい。すなわち、Ca含有量は0%であってもよい。含有される場合、Caは鋼材中のSを硫化物として無害化し、鋼材の耐SSC性を高める。Caが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Ca含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、鋼材中の酸化物が粗大化して、鋼材の耐SSC性が低下する。したがって、Ca含有量は0~0.0100%である。Ca含有量の好ましい下限は0%超であり、さらに好ましくは0.0001%であり、さらに好ましくは0.0003%であり、さらに好ましくは0.0006%である。Ca含有量の好ましい上限は0.0040%であり、さらに好ましくは0.0025%であり、さらに好ましくは0.0020%である。
マグネシウム(Mg)は任意元素であり、含有されなくてもよい。すなわち、Mg含有量は0%であってもよい。含有される場合、Mgは鋼材中のSを硫化物として無害化し、鋼材の耐SSC性を高める。Mgが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Mg含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、鋼材中の酸化物が粗大化して、鋼材の耐SSC性が低下する。したがって、Mg含有量は0~0.0100%である。Mg含有量の好ましい下限は0%超であり、さらに好ましくは0.0001%であり、さらに好ましくは0.0003%であり、さらに好ましくは0.0006%である。Mg含有量の好ましい上限は0.0040%であり、さらに好ましくは0.0025%であり、さらに好ましくは0.0020%である。
ジルコニウム(Zr)は任意元素であり、含有されなくてもよい。すなわち、Zr含有量は0%であってもよい。含有される場合、Zrは鋼材中のSを硫化物として無害化し、鋼材の耐SSC性を高める。Zrが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Zr含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、鋼材中の酸化物が粗大化して、鋼材の耐SSC性が低下する。したがって、Zr含有量は0~0.0100%である。Zr含有量の好ましい下限は0%超であり、さらに好ましくは0.0001%であり、さらに好ましくは0.0003%であり、さらに好ましくは0.0006%である。Zr含有量の好ましい上限は0.0040%であり、さらに好ましくは0.0025%であり、さらに好ましくは0.0020%である。
希土類元素(REM)は任意元素であり、含有されなくてもよい。すなわち、REM含有量は0%であってもよい。含有される場合、REMは鋼材中のSを硫化物として無害化し、鋼材の耐SSC性を高める。REMはさらに、鋼材中のPと結合して、結晶粒界におけるPの偏析を抑制する。そのため、Pの偏析に起因した鋼材の耐SSC性の低下が抑制される。REMが少しでも含有されれば、他の元素含有量が本実施形態の範囲内であっても、上記効果がある程度得られる。しかしながら、REM含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、鋼材中の酸化物が粗大化して、鋼材の耐SSC性が低下する。したがって、REM含有量は0~0.0100%である。REM含有量の好ましい下限は0%超であり、さらに好ましくは0.0001%であり、さらに好ましくは0.0003%であり、さらに好ましくは0.0006%である。REM含有量の好ましい上限は0.0040%であり、さらに好ましくは0.0025%である。
コバルト(Co)は任意元素であり、含有されなくてもよい。すなわち、Co含有量は0%であってもよい。含有される場合、Coはサワー環境において、保護性の腐食被膜を形成し、鋼材への水素の侵入を抑制する。これにより、鋼材の耐SSC性を高める。Coが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Co含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、鋼材の焼入れ性が低下して、鋼材の強度が低下する。したがって、Co含有量は0~0.50%である。Co含有量の好ましい下限は0%超であり、さらに好ましくは0.02%であり、さらに好ましくは0.03%であり、さらに好ましくは0.05%である。Co含有量の好ましい上限は0.45%であり、さらに好ましくは0.40%である。
タングステン(W)は任意元素であり、含有されなくてもよい。すなわち、W含有量は0%であってもよい。含有される場合、Wはサワー環境において、保護性の腐食被膜を形成し、鋼材への水素の侵入を抑制する。これにより、鋼材の耐SSC性を高める。Wが少しでも含有されれば、上記効果がある程度得られる。しかしながら、W含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、鋼材中に粗大な炭化物が生成して、鋼材の低温靭性及び耐SSC性が低下する。したがって、W含有量は0~0.50%である。W含有量の好ましい下限は0%超であり、さらに好ましくは0.02%であり、さらに好ましくは0.03%であり、さらに好ましくは0.05%である。W含有量の好ましい上限は0.45%であり、さらに好ましくは0.40%である。
ニッケル(Ni)は任意元素であり、含有されなくてもよい。すなわち、Ni含有量は0%であってもよい。含有される場合、Niは鋼材の焼入れ性を高め、鋼材の強度を高める。Niはさらに、鋼に固溶して、鋼材の低温靭性を高める。Niが少しでも含有されれば、これらの効果がある程度得られる。しかしながら、Ni含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、局部的な腐食が促進され、鋼材の耐SSC性が低下する。したがって、Ni含有量は0~0.50%である。Ni含有量の好ましい下限は0%超であり、さらに好ましくは0.01%であり、さらに好ましくは0.02%である。Ni含有量の好ましい上限は0.30%であり、さらに好ましくは0.20%であり、さらに好ましくは0.10%である。
銅(Cu)は任意元素であり、含有されなくてもよい。すなわち、Cu含有量は0%であってもよい。含有される場合、Cuは鋼材の焼入れ性を高め、鋼材の強度を高める。Cuが少しでも含有されれば、上記効果がある程度得られる。しかしながら、Cu含有量が高すぎれば、他の元素含有量が本実施形態の範囲内であっても、鋼材の焼入れ性が高くなりすぎ、鋼材の耐SSC性が低下する。したがって、Cu含有量は0~0.50%である。Cu含有量の好ましい下限は0%超であり、さらに好ましくは0.01%であり、さらに好ましくは0.02%であり、さらに好ましくは0.05%である。Cu含有量の好ましい上限は0.35%であり、さらに好ましくは0.25%である。
本実施形態による鋼材は、次の式(1)を満たす。
27×Mn+9×Cr-14×Mo-770×C2+760×C-11×Si2+4×Si>85 (1)
ここで、式(1)中の元素記号には、対応する元素の含有量が質量%で代入される。
本実施形態による鋼材では、転位密度ρと降伏強度σYSとが次の式(2)を満たす。
691<σYS-110×√ρ×10-7≦795 (2)
ここで、式(2)中のσYSには降伏強度がMPaで代入され、ρには転位密度がm-2で代入される。
ΔK×cosθ/λ=0.9/D+2ε×sinθ/λ (3)
ここで、式(3)中において、θ:回折角度、λ:X線の波長、D:結晶子径、を意味する。
ρ=14.4×ε2/b2 (4)
ここで、式(4)中において、bは体心立方構造(鉄)のバーガースベクトル(b=0.248(nm))である。
本実施形態による鋼材の降伏強度σYSは758MPa以上である。降伏強度σYSの上限は、転位密度ρとの関係においてFn2を満たせばよく、特に限定されない。本明細書でいう降伏強度σYSは、引張試験で得られた0.2%オフセット耐力を意味する。本実施形態による鋼材は、式(1)を含む上述の化学組成を有し、転位密度ρと降伏強度σYSとが上述の式(2)を満たすことで、降伏強度σYSが758MPa以上であっても、常温サワー環境及び低温サワー環境における優れた耐SSC性を有する。
本実施形態による鋼材のミクロ組織は、焼戻しマルテンサイト及び焼戻しベイナイトの体積率の合計が90%以上である。ミクロ組織の残部はたとえば、フェライト、又は、パーライトである。上述の化学組成を有する鋼材のミクロ組織が、焼戻しマルテンサイト及び焼戻しベイナイトの体積率の合計が90%以上を含有すれば、本実施形態の他の構成を満たすことを条件に、常温サワー環境及び低温サワー環境において優れた耐SSC性を示す。すなわち、本実施形態では、鋼材が優れた耐SSC性を有していれば、ミクロ組織は焼戻しマルテンサイト及び焼戻しベイナイトの体積率の合計が90%以上であると判断する。
本実施形態による鋼材のミクロ組織において、旧オーステナイト粒径(旧γ粒径)は特に限定されない。鋼材は通常、旧γ粒が微細であれば、降伏強度及び耐SSC性が安定して高まる。そのため、旧γ粒は微細であるのが好ましい。一方、本実施形態による鋼材では、上述のとおり、化学組成においてSi含有量を1.36%以上にまで高める。その結果、鋼材のミクロ組織において、旧γ粒が粗大になりやすい傾向がある。
本実施形態による鋼材の形状は特に限定されない。鋼材はたとえば鋼管、鋼板である。鋼材は、中実材(棒鋼)であってもよい。鋼材が油井用鋼管である場合、好ましい肉厚は9~60mmである。より好ましくは、本実施形態による鋼材は、継目無鋼管である。本実施形態による鋼材が継目無鋼管である場合、肉厚が15mm以上の厚肉の継目無鋼管であっても、常温サワー環境及び低温サワー環境における優れた耐SSC性を有する。
本実施形態による鋼材の耐SSC性は、常温耐SSC性試験及び低温耐SSC性試験によって評価できる。常温耐SSC性試験と低温耐SSC性試験とは、いずれもNACE TM0177-2005 Method Aに準拠した方法で実施する。
常温耐SSC性試験では、5.0質量%塩化ナトリウムと0.5質量%酢酸との混合水溶液(NACE solution A)を、試験溶液とする。本実施形態による鋼材から、丸棒試験片を作製する。鋼材が鋼板である場合、板厚中央部から丸棒試験片を作製する。鋼材が鋼管である場合、肉厚中央部から丸棒試験片を作製する。鋼材が断面円形の棒鋼である場合、R/2位置から丸棒試験片を作製する。丸棒試験片の大きさは、たとえば、径6.35mm、平行部の長さ25.4mmである。なお、丸棒試験片の軸方向は、鋼材の圧延方向と平行である。丸棒試験片に対し、実降伏応力の95%に相当する応力を負荷する。試験容器に24℃の試験溶液を、応力を付加した丸棒試験片が浸漬するように注入し、試験浴とする。試験浴を脱気した後、1atmのH2Sガスを試験浴に吹き込み、試験浴に飽和させる。1atmのH2Sガスを吹き込んだ試験浴を、24℃で720時間、保持する。
常温耐SSC性試験では、5.0質量%塩化ナトリウムと0.5質量%酢酸との混合水溶液(NACE solution A)を、試験溶液とする。本実施形態による鋼材から、丸棒試験片を作製する。鋼材が鋼板である場合、板厚中央部から丸棒試験片を作製する。鋼材が鋼管である場合、肉厚中央部から丸棒試験片を作製する。鋼材が断面円形の棒鋼である場合、R/2位置から丸棒試験片を作製する。丸棒試験片の大きさは、たとえば、径6.35mm、平行部の長さ25.4mmである。なお、丸棒試験片の軸方向は、鋼材の圧延方向と平行である。丸棒試験片に対し、実降伏応力の95%に相当する応力を負荷する。試験容器に24℃の試験溶液を、応力を付加した丸棒試験片が浸漬するように注入し、試験浴とする。試験浴を脱気した後、1atmのH2Sガスを試験浴に吹き込み、試験浴に飽和させる。1atmのH2Sガスを吹き込んだ試験浴を、24℃で720時間、保持する。
常温耐SSC性試験では、酢酸でpH3.5に調整した、5.0質量%塩化ナトリウムと0.4質量%酢酸ナトリウムとの混合水溶液(NACE solution B)を、試験溶液とする。本実施形態による鋼材から、丸棒試験片を作製する。鋼材が鋼板である場合、板厚中央部から丸棒試験片を作製する。鋼材が鋼管である場合、肉厚中央部から丸棒試験片を作製する。鋼材が断面円形の棒鋼である場合、R/2位置から丸棒試験片を作製する。丸棒試験片の大きさは、たとえば、径6.35mm、平行部の長さ25.4mmである。なお、丸棒試験片の軸方向は、鋼材の圧延方向と平行である。丸棒試験片に対し、実降伏応力の95%に相当する応力を負荷する。試験容器に24℃の試験溶液を、応力を付加した丸棒試験片が浸漬するように注入し、試験浴とする。試験浴を脱気した後、0.1atmのH2Sガスと0.9atmのCO2ガスとの混合ガスを試験浴に吹き込み、試験浴に飽和させる。0.1atmのH2Sガスと0.9atmのCO2ガスとの混合ガスを吹き込んだ試験浴を、24℃で720時間、保持する。
本実施形態による鋼材の製造方法を説明する。以下、本実施形態による鋼材の一例として、継目無鋼管の製造方法を説明する。継目無鋼管の製造方法は、素管を準備する工程(準備工程)と、素管に対して焼入れ及び焼戻しを実施して、継目無鋼管とする工程(焼入れ工程及び焼戻し工程)とを備える。なお、本実施形態による製造方法は、以下に説明する製造方法に限定されない。以下、各工程について詳述する。
準備工程では、上述の化学組成を有する中間鋼材を準備する。中間鋼材が上記化学組成を有していれば、中間鋼材の製造方法は特に限定されない。ここでいう中間鋼材は、最終製品が鋼板の場合は、板状の鋼材であり、最終製品が鋼管の場合は素管である。
素材準備工程では、上述の化学組成を有する溶鋼を用いて素材を製造する。素材の製造方法は特に限定されず、周知の方法でよい。具体的には、溶鋼を用いて連続鋳造法により鋳片(スラブ、ブルーム、又は、ビレット)を製造してもよい。溶鋼を用いて造塊法によりインゴットを製造してもよい。必要に応じて、スラブ、ブルーム又はインゴットを分塊圧延して、ビレットを製造してもよい。以上の工程により素材(スラブ、ブルーム、又は、ビレット)を製造する。
熱間加工工程では、準備された素材を熱間加工して中間鋼材を製造する。鋼材が継目無鋼管である場合、中間鋼材は素管に相当する。始めに、ビレットを加熱炉で加熱する。加熱温度は特に限定されないが、たとえば、1100~1300℃である。加熱炉から抽出されたビレットに対して熱間加工を実施して、素管(継目無鋼管)を製造する。熱間加工の方法は、特に限定されず、周知の方法でよい。
焼入れ工程では、準備された中間鋼材(素管)に対して、焼入れを実施する。本明細書において、「焼入れ」とは、A3点以上の中間鋼材を急冷することを意味する。ここで、本明細書において、焼入れを実施する際の急冷直前の中間鋼材の温度を焼入れ温度ともいう。すなわち、本明細書において焼入れ温度とは、熱間加工後に直接焼入れを実施する場合、最終の熱間加工を実施する装置の出側に設置された温度計で測定された、中間鋼材の表面温度に相当する。焼入れ温度とはさらに、熱間加工後に補熱又は再加熱した後、焼入れを実施する場合、補熱又は再加熱を実施する炉の温度に相当する。
焼戻し工程は、上述の焼入れを実施した後、焼戻しを実施する。本明細書において、「焼戻し」とは、焼入れ後の中間鋼材をAc1点以下で再加熱して、保持することを意味する。焼戻し温度は、鋼材の化学組成、及び、得ようとする降伏強度に応じて適宜調整する。つまり、本実施形態の化学組成を有する中間鋼材(素管)に対して、焼戻し温度を調整して、鋼材の降伏強度を、たとえば、758MPa以上(110ksi以上)に調整する。ここで、焼戻し温度とは、焼入れ後の中間鋼材を加熱して、保持する際の炉の温度に相当する。焼戻し時間とは、中間鋼材の温度が所定の焼戻し温度に到達してから、熱処理炉から抽出されるまでの時間を意味する。
低温焼戻し工程における、好ましい焼戻し温度は100~550℃である。低温焼戻し工程における焼戻し温度が高すぎれば、焼戻しの保持中に合金炭化物が微細に分散し、転位密度ρを十分に低減できず、鋼材の耐SSC性が低下する場合がある。一方、低温焼戻し工程における焼戻し温度が低すぎれば、焼戻しの保持中に転位密度ρを低減することができず、鋼材の耐SSC性が低下する場合がある。したがって、低温焼戻し工程における焼戻し温度は100~550℃とするのが好ましい。低温焼戻し工程における焼戻し温度のより好ましい下限は200℃である。低温焼戻し工程における焼戻し温度のより好ましい上限は500℃である。
高温焼戻し工程では、低温焼戻し工程よりも高温で焼戻しを実施することにより、転位密度ρをさらに低減する。ここで、高温焼戻し工程時の中間鋼材において、旧γ粒が粗大すぎれば、転位密度ρを十分に低減できない場合がある。まず、転位の回復(すなわち、転位の消滅)は、異符号の転位対の合体や転位がラスマルテンサイトのブロック境界に相当する大角粒界(方位差15°以上の境界)へ吸収されることで起こる場合が多いと考えられている。一方、旧γ粒が粗大すぎれば、同時にブロック径も大きくなり、転位線の長さも長くなる。ここで、上述のとおり、高温焼戻しを実施した場合、高温で保持される際に合金炭化物が微細に分散する。転位線の長さが長くなった場合、転位の移動時に障害物となる合金炭化物により多く接触する。そのため、転位が移動しにくくなる。その結果、異符号の転位対の合体や、大角粒界への吸収が抑制され、転位の回復が抑制されるものと考えられる。このような旧γ粒径の影響は、低温焼戻し工程であってもブロック内にセメンタイトやε炭化物が析出する場合であれば、同様に生じ得ると予想される。なお、他のメカニズムによって、旧γ粒が粗大な場合に転位密度ρが十分に低減できない可能性もあり得る。しかしながら、上述の化学組成を有する中間鋼材に対して、本実施形態による製造方法を実施すれば、転位密度ρを十分に低減して、転位密度ρと降伏強度σYSとが式(2)を満たすようにすることができる。
上記の焼戻し後の試験番号1-1~1-30の鋼板に対して、以下に説明する引張試験、転位密度測定試験、旧γ粒径測定試験、及び、耐SSC性評価試験を実施した。
試験番号1-1~1-30の鋼板に対して、引張試験を実施した。引張試験はASTM E8/E8M(2013)に準拠して行った。試験番号1-1~1-30の鋼板の板厚中央部から、平行部直径4mm、標点距離20mmの丸棒試験片を作製した。丸棒試験片の軸方向は、鋼板の圧延方向と平行であった。作製した丸棒試験片を用いて、常温(25℃)、大気中にて引張試験を実施して、試験番号1-1~1-30の鋼板の降伏強度σYS(MPa)を得た。なお、本実施例では、引張試験で得られた0.2%オフセット耐力を、降伏強度σYSと定義した。試験番号1-1~1-30について、得られた降伏強度σYSを「σYS(MPa)」として表2に示す。
試験番号1-1~1-30の鋼板に対して、転位密度測定試験を実施した。具体的に、試験番号1-1~1-30の鋼板から、上述の方法で転位密度測定用の試験片を作製した。さらに、試験番号1-1~1-30の試験片を用いて、上述の方法で転位密度ρ(m-2)を求めた。試験番号1-1~1-30の鋼板について、求めた転位密度ρを、「転位密度ρ(1014m-2)」として表2に示す。試験番号1-1~1-30の鋼板についてさらに、求めた転位密度ρと、求めた降伏強度σYSと、上述の定義とから求めたFn2を表2に示す。
試験番号1-1~1-30の鋼板に対して、旧γ粒径測定試験を実施した。具体的に、試験番号1-1~1-30の鋼板から、上述の方法で旧γ粒径測定用の試験片を作製した。さらに、試験番号1-1~1-30の試験片を用いて、上述の方法で旧γ粒径(μm)を求めた。試験番号1-1~1-30の鋼板について、求めた旧γ粒径を、「旧γ粒径(μm)」として表2に示す。
試験番号1-1~1-30の鋼板に対して、耐SSC性評価試験を実施した。NACE TM0177-2005 Method Aに準拠した方法によって、耐SSC性を評価した。具体的には、試験番号1-1~1-30の鋼板の板厚中央部から、径6.35mm、平行部の長さ25.4mmの丸棒試験片を作製した。作製した試験片のうち3本に対して、常温耐SSC性試験を実施した。作製した試験片のうち、他の3本に対して、低温耐SSC性試験を実施した。なお、試験片の軸方向は、圧延方向に平行であった。
表2に試験結果を示す。
上記の焼戻し後の試験番号2-1~2-30の鋼板に対して、以下に説明する引張試験、転位密度測定試験、旧γ粒径測定試験、及び、耐SSC性評価試験を実施した。
実施例1と同様の方法で、試験番号2-1~2-30の鋼板に対して、引張試験を実施した。具体的には、試験番号2-1~2-30の鋼板の板厚中央部から、平行部直径4mm、標点距離20mmであり、軸方向が鋼板の圧延方向と平行である丸棒試験片を作製した。作製した丸棒試験片を用いて、常温(25℃)、大気中にてASTM E8/E8M(2013)に準拠した引張試験を実施して、試験番号2-1~2-30の鋼板の降伏強度σYS(MPa)を得た。なお、本実施例では、引張試験で得られた0.2%オフセット耐力を、降伏強度σYSと定義した。試験番号2-1~2-30について、得られた降伏強度σYSを「σYS(MPa)」として表4に示す。
試験番号2-1~2-30の鋼板に対して、転位密度測定試験を実施した。具体的に、試験番号2-1~2-30の鋼板から、上述の方法で転位密度測定用の試験片を作製した。さらに、試験番号2-1~2-30の試験片を用いて、上述の方法で転位密度ρ(m-2)を求めた。試験番号2-1~2-30の鋼板について、求めた転位密度ρを、「転位密度ρ(1014m-2)」として表4に示す。試験番号2-1~2-30の鋼板についてさらに、求めた転位密度ρと、求めた降伏強度σYSと、上述の定義とから求めたFn2を表4に示す。
試験番号2-1~2-30の鋼板に対して、旧γ粒径測定試験を実施した。具体的に、試験番号2-1~2-30の鋼板から、上述の方法で旧γ粒径測定用の試験片を作製した。さらに、試験番号2-1~2-30の試験片を用いて、上述の方法で旧γ粒径(μm)を求めた。試験番号2-1~2-30の鋼板について、求めた旧γ粒径を、「旧γ粒径(μm)」として表4に示す。
試験番号2-1~2-30の鋼板に対して、耐SSC性評価試験を実施した。NACE TM0177-2005 Method Aに準拠した方法によって、耐SSC性を評価した。具体的には、試験番号2-1~2-30の鋼板の板厚中央部から、径6.35mm、平行部の長さ25.4mmの丸棒試験片を作製した。作製した試験片のうち3本に対して、常温耐SSC性試験を実施した。作製した試験片のうち、他の3本に対して、低温耐SSC性試験を実施した。なお、試験片の軸方向は、圧延方向に平行であった。
表4に試験結果を示す。
上記の焼戻し後の試験番号3-1~3-30の鋼板に対して、以下に説明する引張試験、転位密度測定試験、旧γ粒径測定試験、及び、耐SSC性評価試験を実施した。
実施例1と同様の方法で、試験番号3-1~3-30の鋼板に対して、引張試験を実施した。具体的には、試験番号3-1~3-30の鋼板の板厚中央部から、平行部直径4mm、標点距離20mmであり、軸方向が鋼板の圧延方向と平行である丸棒試験片を作製した。作製した丸棒試験片を用いて、常温(25℃)、大気中にてASTM E8/E8M(2013)に準拠した引張試験を実施して、試験番号3-1~3-30の鋼板の降伏強度σYS(MPa)を得た。なお、本実施例では、引張試験で得られた0.2%オフセット耐力を、降伏強度σYSと定義した。試験番号3-1~3-30について、得られた降伏強度σYSを「σYS(MPa)」として表6に示す。
試験番号3-1~3-30の鋼板に対して、転位密度測定試験を実施した。具体的に、試験番号3-1~3-30の鋼板から、上述の方法で転位密度測定用の試験片を作製した。さらに、試験番号3-1~3-30の試験片を用いて、上述の方法で転位密度ρ(m-2)を求めた。試験番号3-1~3-30の鋼板について、求めた転位密度ρを、「転位密度ρ(1014m-2)」として表6に示す。試験番号3-1~3-30の鋼板についてさらに、求めた転位密度ρと、求めた降伏強度σYSと、上述の定義とから求めたFn2を表6に示す。
試験番号3-1~3-30の鋼板に対して、旧γ粒径測定試験を実施した。具体的に、試験番号3-1~3-30の鋼板から、上述の方法で旧γ粒径測定用の試験片を作製した。さらに、試験番号3-1~3-30の試験片を用いて、上述の方法で旧γ粒径(μm)を求めた。試験番号3-1~3-30の鋼板について、求めた旧γ粒径を、「旧γ粒径(μm)」として表6に示す。
試験番号3-1~3-30の鋼板に対して、耐SSC性評価試験を実施した。NACE TM0177-2005 Method Aに準拠した方法によって、耐SSC性を評価した。具体的には、試験番号3-1~3-30の鋼板の板厚中央部から、径6.35mm、平行部の長さ25.4mmの丸棒試験片を作製した。作製した試験片のうち3本に対して、常温耐SSC性試験を実施した。作製した試験片のうち、他の3本に対して、低温耐SSC性試験を実施した。なお、試験片の軸方向は、圧延方向に平行であった。
表6に試験結果を示す。
Claims (3)
- 質量%で、
C:0.20~0.45%、
Si:1.36~3.20%、
Mn:0.02~1.00%、
P:0.025%以下、
S:0.0100%以下、
Al:0.005~0.100%、
Cr:0.20~1.50%、
Mo:0.36~1.50%、
V:0.01~0.90%、
Ti:0.002~0.050%、
B:0.0001~0.0050%、
N:0.0100%以下、
O:0.0100%以下、
Nb:0~0.030%、
Ca:0~0.0100%、
Mg:0~0.0100%、
Zr:0~0.0100%、
希土類元素:0~0.0100%、
Co:0~0.50%、
W:0~0.50%、
Ni:0~0.50%、
Cu:0~0.50%、及び、
残部がFe及び不純物からなり、式(1)を満たし、
降伏強度σYSが758MPa以上であり、
降伏強度σYSと転位密度ρとが式(2)を満たす、
鋼材。
27×Mn+9×Cr-14×Mo-770×C2+760×C-11×Si2+4×Si>85 (1)
691<σYS-110×√ρ×10-7≦795 (2)
ここで、式(1)中の元素記号には、対応する元素の含有量が質量%で代入される。式(2)中のσYSには降伏強度がMPaで代入され、ρには転位密度がm-2で代入される。 - 請求項1に記載の鋼材であって、
Nb:0.002~0.030%、
Ca:0.0001~0.0100%、
Mg:0.0001~0.0100%、
Zr:0.0001~0.0100%、
希土類元素:0.0001~0.0100%、
Co:0.02~0.50%、
W:0.02~0.50%、
Ni:0.01~0.50%、及び、
Cu:0.01~0.50%からなる群から選択される1元素以上を含有する、
鋼材。 - 請求項1又は請求項2に記載の鋼材であって、
前記鋼材は油井用鋼管である、
鋼材。
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| MX2023005204A MX2023005204A (es) | 2020-11-11 | 2021-10-29 | Material de acero adecuado para su uso en ambientes amargos. |
| US18/044,249 US20230366070A1 (en) | 2020-11-11 | 2021-10-29 | Steel material suitable for use in sour environment |
| JP2022506848A JP7211554B2 (ja) | 2020-11-11 | 2021-10-29 | サワー環境での使用に適した鋼材 |
| EP21891688.0A EP4245866A4 (en) | 2020-11-11 | 2021-10-29 | Steel material suitable for use in sour environment |
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| EP (1) | EP4245866A4 (ja) |
| JP (1) | JP7211554B2 (ja) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117026079A (zh) * | 2023-08-02 | 2023-11-10 | 邯郸新兴特种管材有限公司 | 一种屈服强度大于1425MPa的低合金高强钢无缝钢管及生产方法 |
| JP7564498B1 (ja) * | 2023-04-06 | 2024-10-09 | 日本製鉄株式会社 | 鋼材 |
| WO2024209910A1 (ja) * | 2023-04-06 | 2024-10-10 | 日本製鉄株式会社 | 鋼材 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| PL2762582T3 (pl) * | 2011-09-30 | 2019-08-30 | Nippon Steel & Sumitomo Metal Corporation | Blacha stalowa cienka o dużej wytrzymałości cynkowana z przeżarzaniem o dużej hartowności przy obróbce termicznej, stopowa blacha stalowa cienka cynkowana z przeżarzaniem o dużej wytrzymałości oraz sposób ich wytwarzania |
| EP3778970B1 (en) * | 2018-04-09 | 2023-02-22 | Nippon Steel Corporation | Steel material suitable for use in sour environment |
| JP6958746B2 (ja) * | 2018-10-04 | 2021-11-02 | 日本製鉄株式会社 | サワー環境での使用に適した鋼材 |
-
2021
- 2021-10-29 US US18/044,249 patent/US20230366070A1/en active Pending
- 2021-10-29 MX MX2023005204A patent/MX2023005204A/es unknown
- 2021-10-29 JP JP2022506848A patent/JP7211554B2/ja active Active
- 2021-10-29 WO PCT/JP2021/040108 patent/WO2022102441A1/ja not_active Ceased
- 2021-10-29 EP EP21891688.0A patent/EP4245866A4/en active Pending
- 2021-11-08 AR ARP210103083A patent/AR124011A1/es active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7564498B1 (ja) * | 2023-04-06 | 2024-10-09 | 日本製鉄株式会社 | 鋼材 |
| WO2024209910A1 (ja) * | 2023-04-06 | 2024-10-10 | 日本製鉄株式会社 | 鋼材 |
| CN117026079A (zh) * | 2023-08-02 | 2023-11-10 | 邯郸新兴特种管材有限公司 | 一种屈服强度大于1425MPa的低合金高强钢无缝钢管及生产方法 |
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| US20230366070A1 (en) | 2023-11-16 |
| AR124011A1 (es) | 2023-02-01 |
| JP7211554B2 (ja) | 2023-01-24 |
| EP4245866A4 (en) | 2024-07-31 |
| JPWO2022102441A1 (ja) | 2022-05-19 |
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