EP2857530B1 - Herstellungsverfahren für ein nahtloses rohr aus hochfestem rostfreiem stahl zur verwendung als ölbohrrohr - Google Patents
Herstellungsverfahren für ein nahtloses rohr aus hochfestem rostfreiem stahl zur verwendung als ölbohrrohr Download PDFInfo
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- EP2857530B1 EP2857530B1 EP13796392.2A EP13796392A EP2857530B1 EP 2857530 B1 EP2857530 B1 EP 2857530B1 EP 13796392 A EP13796392 A EP 13796392A EP 2857530 B1 EP2857530 B1 EP 2857530B1
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- 229910001220 stainless steel Inorganic materials 0.000 title claims description 16
- 239000010935 stainless steel Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000003129 oil well Substances 0.000 title description 7
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
- C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
- C21D9/085—Cooling or quenching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
Definitions
- the present invention relates to a manufacturing method for a seamless steel tube for oil country tubular goods, in particular, to a manufacturing method for a high-strength seamless stainless steel tube with both excellent low-temperature toughness and excellent corrosion resistance.
- 13%Cr martensitic stainless steel tubes have been used as steel tubes for oil country tubular goods in the past.
- ordinary 13%Cr martensitic stainless steel cannot be used in an environment containing a large amount of Cl - and having a high temperature of higher than 100°C.
- duplex stainless tubes have been used.
- duplex stainless tubes contain a large amount of alloying chemical elements and are poor in terms of hot formability, duplex stainless tubes can be manufactured by only using particular kinds of hot processing and are expensive.
- Patent Literature 1 describes a method for manufacturing a high-strength stainless steel tube for oil country tubular goods with excellent corrosion resistance, the method including making a steel tube material having a chemical composition including, by mass%, C: 0.005% to 0.05%, Si: 0.05% to 0.5%, Mn: 0.2% to 1.8%, Cr: 15.5% to 18%, Ni: 1.5% to 5%, Mo: 1% to 3.5%, V: 0.02% to 0.2%, N: 0.01% to 0.15%, and O: 0.006% or less, in which relational expressions (1) and (2) below are satisfied, into a steel tube having a specified size by performing hot processing for tube making, cooling the tube down to room temperature at a cooling rate equal to or more than an air-cooling rate after tube making has been performed and performing quenching-tempering on the tube by reheating the tube up to a temperature of 850°C or higher, by subsequently cooling the heated tube down to a temperature of 100°C or lower at
- Patent Literature 1 a high-strength stainless steel tube for oil country tubular goods having sufficient corrosion resistance effective even in an intense corrosion environment having increased concentrations of CO 2 , Cl - and so forth and an increased temperature of up to about 200°C in which 13%Cr martensitic stainless steel cannot be used can be stably manufactured.
- Patent Literature 2 describes a method for manufacturing a stainless steel tube, the method including making a billet having a chemical composition containing, by mass%, C: 0.001% to 0.05%, Si: 0.05% to 1%, Mn: 2% or less, Cr: 16% to 18%, Ni: 3.5% to 7%, Mo: more than 2% and 4% or less, Cu: 1.5% to 4%, rare-earth element: 0.001% to 0.3%, sol.Al: 0.001% to 0.1%, Ca: 0.0001% to 0.3%, N: 0.05% or less and O: 0.05% or less, or further containing one or more selected from the group consisting of Ti: 0.5% or less, Zr: 0.5% or less, Hf: 0.5% or less and V: 0.5% or less into a steel tube by performing hot processing and then performing quenching-tempering on the steel tube.
- Patent Literature 2 a stainless steel tube for oil country tubular goods having not only sufficient corrosion resistance effective even in an intense corrosion environment having a high temperature of up to about 230°C but also high strength can be manufactured.
- US 2012/0031530 A1 discloses a further method for manufacturing a stainless steel pipe for oil well.
- An object of the present invention is, by solving the problems in conventional techniques described above, to provide a high-strength seamless stainless steel tube for oil country tubular goods having a wall thickness of more than 25.4 mm, having not only a high strength of a 110 ksi (758 MPa) grade yield stress or more but also a high toughness of 40 J or more in terms of absorbed energy vE -10 determined by performing a Charpy impact test at a test temperature of -10°C, and, further, having excellent corrosion resistance and a method for manufacturing the steel tube.
- excellent corrosion resistance refers to a case where a tube has excellent CO 2 corrosion resistance effective even in a corrosion environment having a high temperature of 230°C or higher and containing CO 2 and Cl - .
- the present inventors diligently conducted investigations regarding various factors having an influence on toughness, and, as a result, found that it is necessary to form a microstructure having a decreased grain diameter in order to enhance the toughness of a stainless steel tube having a thick wall.
- a ferrite phase crystallizes at a time of solidification, and some of the ferrite phase transforms into an austenite phase when the stainless steel is cooled down to room temperature.
- the present inventors thought of using a spacing GSI (grain size index) value between various phases such as a ferrite phase and an austenite phase (or a martensite phase) as an index expressing the degree of a decrease in the grain diameter of a microstructure and found that, in the case of a stainless steel tube having a chemical composition containing 16% to 18% of Cr and about 2% to 6% of Ni, there is an enhance in toughness by decreasing a GSI value, that is, by decreasing the spacing between various phases.
- GSI grain size index
- Steel materials (billets) having a chemical composition containing, by mass%, 0.026%C-0.20%Si-0.24%Mn-0.01%P-0.001%S-16.7%Cr-4.11%Ni-0.027%V-2.13%Mo-1.06%W-0.51%Cu-0.02%Al-0.051%N and the balance being Fe and inevitable impurities were heated at various heating temperatures.
- a piercer mill, an elongator mill, a plug mill and so forth at various temperatures with various rolling reductions seamless steel tubes having an outer diameter of 297 mm ⁇ and a wall thickness of 26 to 34 mm were made and cooled down to room temperature by performing air-cooling.
- a microstructure was observed using an optical microscope (at a magnification of 400 times).
- a GSI value was determined as an index representing the degree of a decrease in the grain diameter of a microstructure.
- the GSI value was determined by counting the number of ferrite-martensite grain boundaries per unit length (line/mm) in the wall thickness direction using the obtained microstructure photograph.
- Fig. 1 indicates that it is necessary to decrease the grain diameter of a microstructure to GSI: 120 or more in order to achieve toughness of vE -10 : 40 J or more.
- the present inventors confirmed that a decrease in the grain diameter of a microstructure to GSI: 120 or more can be achieved by performing hot rolling under conditions such that the total rolling reduction in a temperature range of 1100°C to 900°C is 30% or more.
- hot rolling including piercing rolling where a slab is heated at an ordinary heating temperature (1100°C to 1250°C
- a temperature range of 1100°C to 900°C corresponds to rolling using an elongator mill and a plug mill or an mandrel mill.
- Fig. 1 is a graph illustrating the relationship between absorbed energy vE -10 in a Charpy impact test and a GSI value.
- a seamless steel tube is manufactured by heating a steel material and by performing hot rolling including piercing rolling.
- the steel material used in the present invention has a chemical composition containing C: 0.005% or more and 0.06% or less, Si: 0.05% or more and 0.5% or less, Mn: 0.2% or more and 1.8% or less, P: 0.03% or less, S: 0.005% or less, Cr: 15.5% or more and 18.0% or less, Ni: 1.5% or more and 4.5% or less, V: 0.02% or more and 0.2% or less, Al: 0.002% or more and 0.05% or less, N: 0.01% or more and 0.15% or less, O: 0.006% or less, and further containing one, two or more selected from among Mo: 1.0% or more and 3.5% or less, W: 3.0% or less and Cu: 3.5% or less and the balance being Fe and inevitable impurities, in which relational expressions (1) and (2) below are satisfied: Cr + 0.65 Ni + 0.60 Mo + 0.30 W + 0.55 Cu ⁇ 20 C ⁇ 19.5 (where Cr, Ni, Mo, W, Cu and C: contents (mass%) of chemical elements respectively represented
- C is a chemical element which is related to an increase in the strength of martensitic stainless steel. It is necessary that the C content be 0.005% or more in the present invention. On the other hand, in the case where the C content is more than 0.06%, there is a significant deteriorate in corrosion resistance. Therefore, the C content is limited to 0.005% or more and 0.06% or less, preferably 0.01% or more and 0.04% or less.
- Si 0.05% or more and 0.5% or less
- Si is a chemical element which functions as a deoxidation agent, and Si is added in the amount of 0.05% or more in the present invention.
- the Si content is limited to 0.05% or more and 0.5% or less, preferably 0.1% or more and 0.4% or less.
- Mn 0.2% or more and 1.8% or less
- Mn is a chemical element which increases strength, and Mn is added in the amount of 0.2% or more in order to achieve the desired high strength in the present invention.
- the Mn content is more than 1.8%, there is a negative influence on toughness. Therefore, the Mn content is limited to 0.2% or more and 1.8% or less, preferably 0.2% or more and 0.8% or less.
- the P content be as small as possible in the present invention.
- the P content is controlled at comparatively low cost without deteriorating corrosion resistance in the case where the P content is 0.03% or less, it is acceptable that the P content is about 0.03% or less. Therefore the P content is limited to 0.03% or less. Since there is an increase in manufacturing cost in the case where the P content is excessively small, it is preferable that the P content be 0.005% or more.
- the S content be as small as possible. However, it is acceptable that the S content is 0.005% or less, because it is possible to manufacture a pipe using normal processes in the case where the S content is 0.005% or less. Therefore, the S content is limited to 0.005% or less. Since there is an increase in manufacturing cost in the case where the S content is excessively small, it is preferable that the S content be 0.0005% or more.
- Cr is a chemical element which enhances corrosion resistance as a result of forming a protective film, and, in particular contributes to an enhance in CO 2 corrosion resistance. It is necessary that the Cr content be 15.5% or more in order to enhance corrosion resistance at a high temperature. On the other hand, in the case where the Cr content is more than 18%, there is a deteriorate in hot formability and there is a decrease in strength. Therefore, the Cr content is limited to 15.5% or more and 18.0% or less, preferably 16.0% or more and 17.5% or less, more preferably 16.5% or more and 17.0% or less.
- Ni is a chemical element which is effective for increasing corrosion resistance by strengthening a protective film and which increases the strength of steel as a result of forming a solid solution. These effects become noticeable in the case where the Ni content is 1.5% or more. On the other hand, in the case where the Ni content is more than 5.0%, since there is a decrease in the stability of a martensite phase, there is a decrease in strength. Therefore, the Ni content is limited to 1.5% or more and 4.5% or less, preferably 3.0% or more and 4.5% or less.
- V 0.02% or more and 0.2% or less
- V contributes to an increase in strength through solid solution strengthening and is effective for increasing resistance to stress corrosion cracking. It is necessary that the V content be 0.02% or more in order to realize these effects. On the other hand, in the case where the V content is more than 0.2%, there is a deteriorate in toughness. Therefore, the V content is limited to 0.02% or more and 0.2% or less, preferably 0.03% or more and 0.08% or less.
- Al 0.002% or more and 0.05% or less
- Al is a chemical element which functions as a deoxidation agent, and it is necessary that the Al content be 0.002% or more in order to realize this effect.
- the Al content is more than 0.05%, since there is an increase in the amount of alumina containing inclusions, there is a deteriorate in ductility and toughness. Therefore, the Al content is limited to 0.002% or more and 0.05% or less, preferably 0.01% or more and 0.04% or less.
- N 0.01% or more and 0.15% or less
- N is a chemical element which markedly enhances pitting corrosion resistance, and it is necessary that the N content be 0.01% or more in the present invention.
- the N content is more than 0.15%, various nitrides are formed and there is a deteriorate in toughness. Therefore, the N content is limited to 0.01% or more and 0.15% or less, preferably 0.02% or more and 0.08% or less.
- O is present in the form of an oxide in steel and has a negative effect on ductility, toughness and so forth. Therefore, it is preferable that the O content be as small as possible. In particular, in the case where the O content is more than 0.006%, there is a significant deteriorate in hot formability, toughness and corrosion resistance. Therefore, the O content is limited to 0.006% or less.
- Mo is a chemical element which contributes to an enhance in corrosion resistance by increasing resistance to pitting corrosion caused by Cl - , and it is necessary that the Mo content be 1.0% or more.
- the Mo content is more than 3.5%, there is a deteriorate in strength and toughness and there is an increase in material cost. Therefore, in the case where Mo is added, the Mo content is limited to 1.0% or more and 3.5% or less, preferably 1.5% or more and 3.0% or less.
- W is a chemical element which contributes to an enhance in corrosion resistance like Mo, and it is preferable that the W content be 0.5% or more.
- the W content is more than 3.0%, there is a deteriorate in toughness and there is an increase in material cost. Therefore, in the case where W is added, the W content is limited to 3.0% or less, preferably 0.5% or more and 2.5% or less.
- Cu Since Cu is effective for suppressing penetration of hydrogen into steel by strengthening a protective film, Cu contributes to an enhance in corrosion resistance. It is preferable that the Cu content be 0.5% or more in order to realize these effects. However, in the case where the Cu content is more than 3.5%, there is a deteriorate in hot formability. Therefore, in the case where Cu is added, the Cu content is limited to 3.5% or less, preferably 0.5% or more and 2.5% or less.
- relational expression (1) By controlling the contents of Cr, Ni, Mo, W, Cu and C so that relational expression (1) is satisfied, there is a significant enhance in corrosion resistance (CO 2 corrosion resistance) at a high temperature (up to 230°C) in a corrosion environment containing CO 2 and Cl - . It is preferable that the value of the left-hand side of relational expression (1) be 20.0 or more from the viewpoint of high-temperature corrosion resistance.
- relational expression (2) By controlling the contents of Cr, Mo, W, Si, C, Mn, Ni, Cu and N so that relational expression (2) is satisfied, there is an enhance in hot workability, and hot workability which is necessary to manufacture a martensitic stainless steel tube can be achieved. It is preferable that the value of the left-hand side of relational expression (2) be 12.5 or more.
- the chemical composition described above is a base chemical composition, and, in addition to the base chemical composition, one or more selected from among Nb: 0.2% or less, Ti: 0.3% or less, Zr: 0.2% or less and B: 0.01% or less and/or Ca: 0.01% or less may be added.
- Nb 0.2% or less
- Ti 0.3% or less
- Zr 0.2% or less
- B 0.01% or less
- Nb, Ti, Zr and B are all chemical elements which increase the strength of steel and enhance resistance to stress corrosion cracking, one or more selected from among these chemical elements may be added as needed. It is preferable that the contents of these chemical elements be respectively Nb: 0.02% or more, Ti: 0.04% or more, Zr: 0.02% or more and B: 0.001% or more in order to realize these effects. On the other hand, in the case where the contents of these chemical elements are respectively Nb: more than 0.2%, Ti: more than 0.3%, Zr: more than 0.2% and B: more than 0.01%, there is a deteriorate in toughness. Therefore, the contents of these chemical elements are respectively limited to Nb: 0.2% or less, Ti: 0.3% or less, Zr: 0.2% or less and B: 0.01% or less.
- Ca is a chemical element which contributes to a morphology control function of sulfides as a result of spheroidizing sulfide containing inclusions
- Ca may be added as needed.
- the Ca content be 0.0005% or more in order to realize this effect.
- the Ca content is more than 0.01%, there is an increase in the amount of oxide containing inclusions, which deteriorates corrosion resistance. Therefore, in the case where Ca is added, it is preferable that the Ca content be 0.01% or less.
- the remainder of the chemical composition other than the constituent chemical elements described above consists of Fe and inevitable impurities.
- molten steel having a specified chemical composition be smelted using a common refining method such as one using a steel converter and that the smelted steel be made into a cast material such as a billet using a common casting method such as a continuous casting method.
- a common refining method such as one using a steel converter
- a common casting method such as a continuous casting method.
- a seamless steel tube is manufactured by heating a steel material having the chemical composition described above, by performing ordinary hot rolling including piercing rolling using a Mannesmann-plug mill method or a Mannesmann-mandrel mill method, and further performing cooling down to room temperature at a cooling rate equal to or more than an air-cooling rate.
- the wall thickness of the seamless steel tube is set to be more than 25.4 mm. It is needless to say that the size of a steel material which is a starting material is controlled to be within an appropriate range in order to achieve a seamless steel tube having such a wall thickness.
- Heating temperature of a steel material 1100°C or higher and 1300°C or lower
- the heating temperature of a steel material In the case where the heating temperature of a steel material is lower than 1100°C, there is an enhance in deformation resistance due to the heating temperature being excessively low and it is difficult to perform hot rolling due to a load on rolling mills being excessively large. On the other hand, in the case where the heating temperature is higher than 1300°C, there is a deteriorate in toughness due to an increase in crystal grain diameter and there is a decrease in yield due to an increase in the amount of scale loss. Therefore, it is preferable that the heating temperature of a steel material be 1100°C or higher and 1300°C or lower, more preferably 1200°C or higher and 1280°C or lower.
- the steel material which has been heated up to the heating temperature descried above is subjected to hot rolling including piercing rolling.
- hot rolling any of an ordinary Mannesmann-plug mill method, in which the steel material is subjected to processing using a piercer mill for performing piercing rolling, a subsequent elongator mill, a plug mill and a realer mill, or, further, a sizing mill in this order, and an ordinary Mannesmann-mandrel mill method, in which the steel material is subjected to processing using a piercer mill for performing piercing rolling, a subsequent mandrel mill and reducer mill in this order, may be used.
- the hot rolling including piercing rolling described above is performed under conditions such that the total rolling reduction in a temperature range of 1100°C to 900°C is 30% or more.
- the spacing between ferrite-austenite (martensite) grain boundaries can be controlled to be small and a decrease in grain diameter can be achieved, which results in an enhance in toughness.
- rolling reduction is controlled in a temperature range out of the range of 1100°C to 900°C, if rolling reduction in the temperature range of 1100°C to 900°C is out of the appropriate range described above, a decrease in grain diameter according to the present invention cannot be achieved.
- the rolling reduction in this temperature range is set to be 30% or more.
- the rolling reduction in the temperature range of 1100°C to 900°C is set to be 30% or more.
- the seamless steel tube which has been manufactured by performing hot rolling for tube making as described above is subsequently subjected to cooling down to room temperature at a cooling rate equal to or more than an air-cooling rate.
- a microstructure including a martensite phase as a main phase can be achieved by performing cooling at a cooling rate equal to or more than an air-cooling rate.
- the cooled steel tube is subsequently subjected to a heat treatment including quenching-tempering.
- the steel tube In quenching, the steel tube is heated up to a heating temperature for quenching of 850°C or higher and 1000°C or lower, and then cooled with water.
- the heating temperature for quenching In the case where the heating temperature for quenching is lower than 850°C, transformation into a martensite does not sufficiently progress, and the desired high strength cannot be achieved. Further, there is concern that intermetallic compounds may be formed and toughness and corrosion resistance may deteriorate.
- the heating temperature for quenching is higher than 1000°C, the fraction of a martensite formed becomes excessively high, and strength becomes excessively high. Therefore, it is preferable that the heating temperature for quenching be 850°C or higher and 1000°C or lower.
- a holding time when heating is performed for quenching there is no particular limitation on a holding time when heating is performed for quenching.
- the holding time be 10 to 30 minutes from the viewpoint of productivity.
- the heating temperature for quenching be 920°C or higher and 980°C or lower.
- tempering is further performed.
- the steel tube is heated up to a tempering temperature of 400°C or higher and 700°C or lower, and then cooled at a cooling rate equal to or more than an air-cooling rate.
- the tempering temperature is lower than 400°C, a sufficient tempering effect cannot be realized.
- the tempering temperature is higher than 700°C, there is a tendency for intermetallic compounds to precipitate, which may deteriorate toughness and corrosion resistance. Therefore, it is preferable that the tempering temperature be 400°C or higher and 700°C or lower.
- the holding time there is no particular limitation on a holding time when heating for tempering is performed. However, it is preferable that the holding time be 20 to 60 minutes from the viewpoint of productivity. Further, it is more preferable that the tempering temperature be 550°C or higher and 650°C or lower.
- tempering described above may be performed without performing quenching on the steel tube which has been subjected to tube making.
- the seamless steel tube which is manufactured using the manufacturing method described above has a chemical composition described above and a microstructure including a martensite phase as a main phase and a second phase consisting of, at volume ratio, 10% or more and 60% or less of a ferrite phase and 0% or more and 10% or less of an austenite phase.
- the steel tube is a thick high-strength seamless stainless steel tube for oil country tubular goods having a wall thickness of more than 25.4 mm and having a microstructure in which a GSI value, which is defined as the number of ferrite-martensite grain boundaries per unit length of a line segment drawn in the wall thickness direction, is 120 or more in the central portion in the wall thickness direction.
- the microstructure includes a martensite phase as a main phase and a second phase consisting of, at volume ratio, 10% or more and 60% or less of a ferrite phase and 0% or more and 10% or less of an austenite phase in order to achieve the desired high strength.
- the volume ratio of a ferrite phase is less than 10%, there is a deteriorate in hot formability.
- the volume ratio of a ferrite phase is more than 60%, there is a deteriorate in strength and toughness.
- the second phase may include 10% or less of an austenite phase other than a ferrite phase, it is preferable that the volume ratio of an austenite phase be as small as possible, including 0%, in order to achieve sufficient strength. In the case where the volume ratio of an austenite phase is more than 10%, it is difficult to achieve the desired high strength.
- the steel tube manufactured according to the present invention has a microstructure including a martensite and a ferrite phase, and, further, a retained austenite phase as described above, in which a GSI value, which is defined as the number of ferrite-martensite grain boundaries per unit length of a line segment drawn in the wall thickness direction, is 120 or more in the central portion in the wall thickness direction.
- a GSI value which is defined as the number of ferrite-martensite grain boundaries per unit length of a line segment drawn in the wall thickness direction, is 120 or more in the central portion in the wall thickness direction.
- a GSI value is a value which can be determined by counting the number (line/mm) of ferrite-martensite grain boundaries in the wall thickness direction using a microstructure photograph taken through the observation of a sample, which has been etched with a vilella's reagent, using an optical microscope (magnification of 100 to 1000 times).
- Molten steels having the chemical compositions given in Table 1 were smelted using a steel converter, and then cast into billets (steel materials having an outer diameter of 260 mm) using a continuous casting method.
- the obtained steel materials were heated at the temperatures given in Table 2, and then made into seamless steel tubes (having an outer diameter of 168.3 to 297 mm ⁇ and a wall thickness of 26 to 34 mm) by performing hot rolling using an ordinary Mannesmann-plug mill method in which the steel material is subjected to hot processing using a piercing mill, an elongator mill, a plug mill and realer mill, or, further, a sizing mill in this order under conditions such that the rolling reduction in a temperature range of 1100°C to 900°C satisfied the conditions given in Table 2. Further, after hot rolling had been performed, cooling was performed under the conditions given in Table 2. The obtained seamless steel tubes were subjected to quenching-tempering under the conditions given in Table 2.
- a microstructure in a cross section in the wall thickness direction which had been polished and etched with a vilella's reagent, was observed using an optical microscope (at a magnification of 100 to 1000 times).
- the kinds of microstructures were identified, and the fraction (volume ratio) of a ferrite phase was calculated by performing image analysis.
- test piece for microstructure observation was etched with a vilella's reagent and observed using an optical microscope (at a magnification of 400 times). Using the taken photograph, the number (line/mm) of ferrite-martensite grain boundaries was counted in the wall thickness direction in order to calculate a GSI value.
- a strip specimen specified by API standard (having a gage length of 50.8 mm) was cut out of the central portion in the wall thickness direction of the obtained steel tube in accordance with API standard so that the tensile direction is the direction of the tube axis.
- tensile properties yield strength YS, tensile strength TS and elongation El
- V-notch test piece (having a thickness of 10 mm) which was cut out of the central portion in the wall thickness direction of the obtained steel tube in accordance with ISO standard so that the longitudinal direction of the test piece was the circumferential direction of the tube
- Charpy impact test was performed under a condition of a test temperature of -10°C in order to determine absorbed energy vE -10 (J).
- the number of the test pieces was 3 for each steel tube, the average value of the three was used as the value for the steel tube.
- a test specimen for a corrosion test (having a thickness of 3 mm, a width of 25 mm and a length of 50 mm) was cut out of the central portion in the wall thickness direction of the obtained steel tube and used for a corrosion test.
- the test specimen was immersed in a 20% NaCl aqueous solution (having a temperature of 230°C with carbon dioxide gas of 3.0 MPa being dissolved in the saturated state) which was contained in an autoclave, for 14 days. After the corrosion test had been performed, by determining the weight of the test specimen, a corrosion rate was calculated from a decrease in weight. In addition, after the corrosion test had been performed, the test specimen was observed using a loupe at a magnification ratio of 50 times in order to observe whether or not pitting corrosion occurred. A case where pitting corrosion of a diameter of 0.2 mm or more was observed was evaluated as a case where pitting corrosion occurred.
- All of the examples of the present invention had a high strength of 758 MPa (110 ksi) or more and a high toughness of vE -10 (J) : 40 J or more despite having a large wall thickness.
- vE -10 vE -10
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Claims (1)
- Ein Verfahren zum Herstellen eines hochfesten nahtlosen rostfreien Stahlrohrs für ÖI-Land-Rohrwaren mit einer Wanddicke von mehr als 25,4 mm, wobei das Verfahren umfasst: Erwärmen eines Stahlmaterials; Warmwalzen einschließlich Dornwalzen des Stahlmaterials zu einem nahtlosen Stahlrohr; und Abkühlen des nahtlosen Stahlrohrs auf Raumtemperatur mit einer Abkühlrate, die gleich oder größer als eine Luftkühlrate ist, wobei das Stahlmaterial eine chemische Zusammensetzung in Masse-% aufweist, bestehend aus
C: 0,005% oder mehr und 0,06% oder weniger, Si: 0,05% oder mehr und 0,5% oder weniger,
Mn: 0,2% oder mehr und 1,8% oder weniger, P: 0,03% oder weniger,
S: 0,005% oder weniger, Cr: 15,5% oder mehr und 18,0% oder weniger,
Ni: 1,5% oder mehr und 4,5% oder weniger, V: 0,02% oder mehr und 0,2% oder weniger,
Al: 0,002% oder mehr und 0,05% oder weniger, N: 0,01% oder mehr und 0,15% oder weniger, O: 0,006% oder weniger, und
ferner bestehend aus einem, zweien oder mehreren, ausgewählt aus Mo: 1,0% oder mehr und 3,5% oder weniger, W: 3,0% oder weniger und Cu: 3,5% oder weniger, gegebenenfalls weiter einen oder mehrere ausgewählt aus Nb: 0,2% oder weniger, Ti: 0,3% oder weniger, Zr: 0,2% oder weniger und B: 0,01 % oder weniger und Ca: 0,01% oder weniger, und der Rest sind Fe und unvermeidbare Verunreinigungen, wobei die relationalen Ausdrücke (1) und (2) wie unten angegeben erfüllt sind, wird das Warmwalzen einschließlich Dornwalzen unter solchen Bedingungen durchgeführt, dass die gesamte Walzreduktion in einem Temperaturbereich von 1100°C bis 900°C 30% oder mehr beträgt, und nachdem das gewalzte Stahlrohr auf Raumtemperatur abgekühlt ist, wird Abschrecken-Anlassen oder Anlassen durchgeführt:
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CN102300574A (zh) * | 2009-01-26 | 2011-12-28 | 神经研究公司 | 新的吲哚基-*二唑基-二氮杂二环壬烷衍生物及它们的医药和诊断用途 |
AR076669A1 (es) * | 2009-05-18 | 2011-06-29 | Sumitomo Metal Ind | Acero inoxidable para pozos de petroleo, tubo de acero inoxidable para pozos de petroleo, y metodo de fabricacion de acero inoxidable para pozos de petroleo |
WO2011021396A1 (ja) * | 2009-08-21 | 2011-02-24 | 住友金属工業株式会社 | 厚肉継目無鋼管の製造方法 |
MY158405A (en) * | 2010-04-28 | 2016-10-14 | Sumitomo Metal Ind | Seamless steel pipe for steam injection and method for manufacturing the same |
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2012
- 2012-05-31 JP JP2012125126A patent/JP5488643B2/ja active Active
-
2013
- 2013-05-30 RU RU2014153558/02A patent/RU2584100C1/ru active
- 2013-05-30 IN IN2395KON2014 patent/IN2014KN02395A/en unknown
- 2013-05-30 BR BR112014029392-9A patent/BR112014029392B1/pt active Search and Examination
- 2013-05-30 EP EP13796392.2A patent/EP2857530B1/de active Active
- 2013-05-30 AU AU2013268908A patent/AU2013268908B2/en not_active Ceased
- 2013-05-30 WO PCT/JP2013/003411 patent/WO2013179667A1/ja active Application Filing
- 2013-05-30 CN CN201380028317.XA patent/CN104379774B/zh active Active
- 2013-05-30 ES ES13796392T patent/ES2708275T3/es active Active
- 2013-05-30 US US14/403,731 patent/US20150101711A1/en not_active Abandoned
- 2013-05-30 CA CA2872342A patent/CA2872342C/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1662015A1 (de) * | 2003-08-19 | 2006-05-31 | JFE Steel Corporation | Rohr aus hochfestem nichtrostendem stahl mit hervorragender korrosionsbeständigkeit zur verwendung in erdölbohrlöchern und herstellungsverfahren dafür |
Also Published As
Publication number | Publication date |
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CN104379774B (zh) | 2017-04-26 |
CA2872342C (en) | 2018-07-17 |
JP5488643B2 (ja) | 2014-05-14 |
ES2708275T3 (es) | 2019-04-09 |
BR112014029392A2 (pt) | 2017-06-27 |
EP2857530A1 (de) | 2015-04-08 |
CA2872342A1 (en) | 2013-12-05 |
IN2014KN02395A (de) | 2015-05-01 |
BR112014029392B1 (pt) | 2019-09-24 |
RU2584100C1 (ru) | 2016-05-20 |
WO2013179667A1 (ja) | 2013-12-05 |
EP2857530A4 (de) | 2015-11-04 |
CN104379774A (zh) | 2015-02-25 |
US20150101711A1 (en) | 2015-04-16 |
AU2013268908A1 (en) | 2014-11-20 |
AU2013268908B2 (en) | 2016-01-28 |
JP2013249516A (ja) | 2013-12-12 |
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