WO2020110597A1 - 二相ステンレス継目無鋼管およびその製造方法 - Google Patents
二相ステンレス継目無鋼管およびその製造方法 Download PDFInfo
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- WO2020110597A1 WO2020110597A1 PCT/JP2019/042969 JP2019042969W WO2020110597A1 WO 2020110597 A1 WO2020110597 A1 WO 2020110597A1 JP 2019042969 W JP2019042969 W JP 2019042969W WO 2020110597 A1 WO2020110597 A1 WO 2020110597A1
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- pipe
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 95
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Images
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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
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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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
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/13—Modifying the physical properties of iron or steel by deformation by hot working
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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
- 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
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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
- 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
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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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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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
- C22C38/002—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
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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
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- 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
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- 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
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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
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- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D3/00—Straightening or restoring form of metal rods, metal tubes, metal profiles, or specific articles made therefrom, whether or not in combination with sheet metal parts
- B21D3/14—Recontouring
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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
Definitions
- the present invention relates to a duplex stainless steel pipe having excellent tensile yield strength and corrosion resistance in the pipe axis direction and a small difference between the tensile yield strength and the compression yield strength in the pipe axis direction, and a method for producing the same.
- the difference between the tensile yield strength and the compressive yield strength in the pipe axis direction is small means that the compressive yield strength in the pipe axis direction/the tensile yield strength in the pipe axis direction is in the range of 0.85 to 1.15.
- Seamless steel pipes for oil and gas well mining are important for their corrosion resistance to withstand high corrosive environments under high temperature and high pressure, and their high strength characteristics to withstand their own weight and high pressure when connected to a high depth.
- the amount of addition of corrosion resistance improving elements such as Cr, Mo, W and N is important for steel.
- SUS329J3L containing 22% Cr, SUS329J4L containing 25% Cr, and a large amount of Mo added Duplex stainless steel such as ISO S32750 and S32760 is used.
- the most important value is tensile yield strength in the pipe axis direction, and this value is the representative value of product strength specifications.
- the reason for this is that the ability to withstand the tensile stress due to its own weight when connecting the pipes to a high depth is of utmost importance, and it has a sufficiently large axial tensile yield strength for the tensile stress due to its own weight. It suppresses plastic deformation and prevents damage to the passive film, which is important for maintaining the corrosion resistance of the pipe surface.
- the tensile yield strength in the pipe axis direction is the most important, but the compressive yield strength in the pipe axis direction is also important for the connecting part of the pipe.
- Pipes for oil wells and gas wells cannot be welded for connection, but rather screwed for the purpose of fire prevention and repeated insertion and removal. Therefore, a compressive stress in the pipe axis direction is generated in the thread according to the fastening force. Therefore, the axial compressive yield strength that can withstand this compressive stress is important.
- Duplex stainless steel is composed of two phases, a ferrite phase and an austenite phase with a low yield strength in terms of crystal structure in the structure, and the strength required for oil country tubular goods cannot be ensured in the state of hot forming or heat treatment. Therefore, the pipes used for oil wells utilize the dislocation strengthening by various cold rolling to enhance the tensile yield strength in the pipe axial direction.
- Cold rolling methods for pipes used for oil wells are limited to two types, cold drawing rolling and cold pilger rolling. Even NACE (National Association of Corrosion Engineers), which is an international standard regarding the use of oil well pipes, is cold drawing. Definitions are given only for (cold drawing rolling) and Cold pilgering (cold pilger rolling).
- any cold rolling is a work of reducing the wall thickness and extending it in the longitudinal direction of the pipe by shrinking
- the dislocation strengthening by strain works most effectively for improving the tensile yield strength in the longitudinal direction of the pipe.
- the compressive yield strength in the pipe axial direction is reduced by about 20% because a strong Bauschinger effect is generated in the pipe axial direction.
- the screw fastening part where the axial compressive yield strength characteristic is required, it is common to design the strength with a low yield strength on the assumption that the Bauschinger effect occurs, and this design had a rate-limiting effect on the overall product specifications. ..
- Patent Document 1 C: 0.008 to 0.03%, Si: 0 to 1%, Mn: 0.1 to 2%, Cr: 20 to 35%, and Ni in mass%. : 3 to 10%, Mo: 0 to 4%, W: 0 to 6%, Cu: 0 to 3%, N: 0.15 to 0.35%, the balance consisting of iron and impurities.
- a duplex stainless steel pipe characterized in that the tensile yield strength YS CT in the pipe circumferential direction and the compressive yield strength YS CC in the pipe circumferential direction satisfy predetermined formulas.
- Patent Document 1 does not consider corrosion resistance.
- the present invention has been made in view of the above circumstances, with excellent corrosion resistance, high tensile strength in the pipe axial direction, and a small difference between tensile yield strength and compressive yield strength in the axial direction of the pipe is a two-phase stainless steel joint.
- An object of the present invention is to provide a steelless pipe and a manufacturing method thereof.
- duplex stainless steel by increasing the solid solution amount of Cr and Mo in the steel, a high corrosion resistant film is formed and the local progress of corrosion is suppressed.
- Cr and Mo which are the main corrosion resistance elements, are all ferrite phase forming elements, and the phase fraction cannot be set to an appropriate two-phase state by simply increasing the addition amount. Therefore, it is necessary to add an appropriate amount of the austenite phase forming element.
- the duplex stainless seamless steel pipe is subjected to solid solution heat treatment, which is a high temperature heat treatment of 1000°C or higher after hot forming in order to dissolve the corrosion resistant element in the steel and form the phase fraction in an appropriate two-phase state. It is used after going. After that, if higher strength is required, cold rolling is used to strengthen the dislocations.
- solid solution heat treatment a high temperature heat treatment of 1000°C or higher after hot forming in order to dissolve the corrosion resistant element in the steel and form the phase fraction in an appropriate two-phase state. It is used after going.
- cold rolling is used to strengthen the dislocations.
- the product is processed by solution heat treatment or cold rolling, the elements effective for corrosion resistance are solid-solved in the steel, and it shows high corrosion resistance performance. High strength can be obtained. Further, the strength improving effect by solid solution strengthening of N becomes more remarkable by cold working.
- N has a small atomic size, and easily diffuses even at a low temperature heat treatment and combines with surrounding corrosion resistant elements to form a nitride, which nullifies the effect as a corrosion resistant element.
- the precipitated nitrides are mostly of the corrosion resistant elements Cr and Mo, but since these precipitates are large in size and are more difficult to disperse and precipitate, the strength improving effect is greater than that of N dissolved in steel. Inferior That is, it is desirable to reduce the amount of N in order to suppress the deterioration of corrosion resistance performance, but on the other hand, the reduction of the addition of N also reduces the amount of N effective for solution strengthening at the same time.
- the nitride is formed at a temperature higher than the maximum temperature (1000° C. or less) formed by the corrosion resistant elements Cr and Mo-based nitrides, and solid solution occurs before the formation of the Cr and Mo-based nitrides. It is possible to control the consumption of the corrosion resistant element by fixing and controlling the amount of N. Next, the strengthening will be described. Ti, Al, V, and Nb added to control the amount of solute N form nitrides, but their size is very fine and they precipitate uniformly in the steel, so precipitation strengthening (dispersion strengthening) Contributes to the improvement of strength.
- the duplex stainless seamless steel pipe according to any one of [1] to [3], containing two or more kinds.
- the present invention it is possible to obtain a duplex stainless steel pipe having high corrosion resistance and high strength, and having a small difference between the tensile yield strength in the pipe axial direction and the compressive yield strength in the pipe circumferential direction. Therefore, with the duplex stainless seamless steel pipe of the present invention, it is possible to guarantee the crushing strength, which is often evaluated by the improvement in the design freedom of the screw fastening portion and the tensile yield strength in the pipe axial direction.
- FIG. 1 is a schematic view showing bending and bending back processing in the pipe circumferential direction.
- C is an austenite phase forming element, and when contained in an appropriate amount, it helps optimize the phase fraction. However, an excessive content leads to a decrease in corrosion resistance due to the formation of carbide. Therefore, the upper limit of C is 0.08%. Regarding the lower limit, a decrease in the austenite phase due to a decrease in the amount of C does not need to be particularly provided because it can be covered by other austenite phase forming elements, but if the amount of C is too low, the decarburization cost during melting increases, Set to 0.005% or more.
- Si 0.01-1.0% Since Si has a deoxidizing effect on steel, it is effective to contain an appropriate amount in molten steel. However, when a large amount of Si is contained, it remains in the steel, which deteriorates workability and low temperature toughness. Therefore, the upper limit of Si is 1.0%. The lower limit is set to 0.01% or more because excessive reduction of Si after deoxidation leads to an increase in manufacturing cost. It is preferable that Si is 0.2 to 0.8% from the viewpoint of simultaneously obtaining a sufficient deoxidizing action and suppressing side effects due to excessive residual in steel.
- Mn 0.01-10.0% Mn is a strong austenite phase forming element and is cheaper than other austenite phase forming elements. Even if low-temperature heat treatment is performed, corrosion-resistant elements such as C and N are not consumed. Therefore, in order to bring the austenite phase fraction of the duplex stainless seamless steel pipe into an appropriate two-phase state when C and N are reduced, it is necessary to contain 0.01% or more. On the other hand, excessive Mn content lowers the low temperature toughness. Therefore, it is 10.0% or less. It is preferably less than 1.0% so as not to impair the low temperature toughness.
- Mn is effective for detoxifying S, which is an impurity element mixed in molten steel, and Mn is 0.01 because it has the effect of fixing S as MnS, which significantly deteriorates the corrosion resistance and toughness of steel with a small amount of addition. Contains at least %.
- Cr 20-35% Cr is the most important element that strengthens the passivation film of steel and enhances corrosion resistance. 20% or more Cr content is required for duplex stainless seamless steel pipes used in harsh corrosive environments. As the amount of Cr increases, it contributes to the improvement of corrosion resistance. However, if the content exceeds 35%, the embrittlement phase precipitates in the process of melting and solidification and cracks occur throughout, making subsequent molding difficult. Therefore, the upper limit is 35%. From the viewpoint of ensuring both corrosion resistance and manufacturability, the preferable range is 22 to 28%.
- Ni 1-15%
- Mn which is an inexpensive austenite phase forming element
- the lower limit is 1%
- Ni is the most expensive element among the other austenite phase forming elements, and an increase in the content leads to an increase in manufacturing cost. Therefore, it is not preferable to contain a large amount unnecessarily. Therefore, the upper limit is 15%.
- positive addition of Ni is effective, and the range of 5 to 13% is preferable.
- Mo 0.5-6.0% Mo enhances the pitting corrosion resistance of steel depending on the content. Therefore, an appropriate amount is added according to the corrosive environment. On the other hand, an excessive Mo content causes precipitation of an embrittlement phase during molten steel to solidification, causes a large amount of cracks in the solidified structure, and greatly impairs subsequent molding stability. Therefore, the upper limit is 6.0%.
- the content of Mo improves pitting corrosion resistance depending on the content, but 0.5% or more is necessary to maintain stable corrosion resistance in a sulfide environment.
- the preferable range is 1.0 to 5.0% from the viewpoint of achieving both the corrosion resistance and manufacturing stability required for a duplex stainless steel pipe.
- N 0.150 to less than 0.400%
- N is a strong austenite phase forming element and is inexpensive. Further, if it forms a solid solution in steel, it is an element that is useful for improving corrosion resistance and strength, so it is actively used.
- the upper limit is made less than 0.400%.
- the lower limit of N should be 0.150% or more.
- it is essential to add any one of Ti, Al, V, and Nb, or a composite addition, and these additives are finely formed as nitrides during the cooling process after solidification to obtain a strength improving effect. If the N content is too small, it becomes difficult to obtain a stable strength improving effect, so it is necessary to set the lower limit to 0.150% or more. Further, a more preferable range for obtaining a sufficient strength improving effect is 0.155 to 0.320%.
- Ti 0.0001 to 0.3%, Al: 0.0001 to 0.3%, V: 0.005 to 1.5%, Nb: 0.005 to less than 1.5%
- One or more selected from Ti, Al, V and Nb When contained, fine nitrides are generated during cooling from melting to improve strength, and at the same time, it becomes possible to appropriately control the amount of dissolved N in steel. As a result, it is possible to suppress the phenomenon that corrosion resistance and strength are deteriorated due to corrosion-resistant elements such as Cr and Mo being consumed as nitrides and coarsely deposited.
- the lower limit of the content for obtaining this effect is Ti: 0.0001%, Al: 0.0001%, V: 0.005%, Nb: 0.005% or more.
- Ti 0.3% or less, Al: 0.3% or less, V: 1.5% or less, and Nb: less than 1.5%, respectively.
- the present invention can achieve both corrosion resistance and strength.
- the content of Ti, Al, V, Nb alone or in combination is too large, the fixed N will be insufficient and the contained elements will remain in the steel, which is not a problem in terms of product properties. Even in such a case, hot moldability and the like become unstable. Therefore, as a more preferable range, the upper limits of the content are Ti: 0.0500% or less, Al: 0.150% or less, V: 0.60% or less, and Nb: 0.60% or less. Whether Ti, Al, V, or Nb is contained singly or in combination, if it is contained within the respective preferable ranges and satisfies the formula (1) described later, the corrosion resistance, strength and hot formability are further stabilized. be able to.
- N, Ti, Al, V and Nb are contained so as to satisfy the following formula (1). 0.150>N-(1.58Ti+2.70Al+1.58V+1.44Nb) ⁇ (1)
- N, Ti, Al, V, and Nb are the contents (mass %) of each element. (However, if it is not contained, the content is 0%.)
- Stable corrosion resistance and high strength can be achieved by satisfying the following formula (1). That is, the content of Ti, Al, V, and Nb according to the present invention should be the optimum amount with respect to the N content added to the steel. Corrosion resistance and strength are not stable due to insufficient precipitation.
- Formula (1) is a formula that can be optimized for the amount of N contained when Ti, Al, V, and Nb are contained individually or in combination, and stable corrosion resistance and strength can be obtained. become.
- the balance is Fe and inevitable impurities.
- the unavoidable impurities include P: 0.05% or less, S: 0.05% or less, and O: 0.01% or less.
- P, S, and O are impurities that are inevitably mixed during smelting. When the residual amount of these elements is too large as impurities, various problems such as deterioration of hot workability, corrosion resistance and low temperature toughness occur. Therefore, it is necessary to manage P: 0.05% or less, S: 0.05% or less, and O: 0.01% or less.
- the present invention may optionally contain the elements described below.
- W 0.1 to 6.0%
- Cu 0.1 to 4.0%
- selected 1 or 2 types W 0.1 to 6.0%
- W enhances pitting corrosion resistance depending on the content, but if it is excessively contained, workability is impaired during hot working and manufacturing stability is impaired. Therefore, when W is contained, the upper limit is 6.0%.
- the content of W improves the pitting corrosion resistance depending on the content, and thus there is no need to set a lower limit, but a content of 0.1% or more is preferable for the reason of stabilizing the corrosion resistance performance of the duplex stainless seamless steel pipe. From the viewpoint of corrosion resistance and manufacturing stability required for duplex stainless seamless steel pipe, 1.0 to 5.0% is a more preferable range.
- Cu 0.1-4.0%
- Mn and Ni which are other austenite phase forming elements, should be positively utilized when the corrosion resistance is insufficient.
- Cu is set to 4.0% or less.
- the lower limit of the content does not have to be specified in particular, but the corrosion resistance effect can be obtained if the content is 0.1% or more. From the viewpoint of improving both corrosion resistance and hot workability, the addition amount of 1.0 to 3.0% is a more preferable range.
- the present invention may further appropriately contain the elements described below, if necessary.
- B 0.0001 to 0.010%
- Zr 0.0001 to 0.010%
- Ca 0.0001 to 0.010%
- Ta 0.0001 to 0.3%
- REM 0.0001 to 0.010% selected from 1 or 2 types B, Zr
- Ca or REM is added in a very small amount, it improves the bond strength of the grain boundary and changes the form of the oxide on the surface to improve hot workability and formability.
- Duplex stainless steel seamless steel pipes are generally difficult-to-machine materials, so rolling flaws and defective shapes are likely to occur due to the processing amount and processing form, but in the case of molding conditions that cause such problems. These elements are effective.
- the lower limit of the addition amount it is not necessary to set the lower limit of the addition amount, but when it is contained, 0.0001% or more can provide an effect of improving workability and moldability.
- the upper limits of the amounts added are 0.010% for B, Zr, Ca, and REM, respectively.
- Ta When Ta is added in a small amount, it suppresses the transformation into the brittle phase and improves hot workability and corrosion resistance at the same time. Therefore, when Ta is contained, the content is 0.0001% or more. These elements are effective when the embrittlement phase stays in the stable temperature region for a long time during hot working and subsequent cooling.
- the addition amount is too large, the alloy cost increases, so the upper limit is made 0.3% when Ta is contained.
- Fig. 9 of the Technical Bulletin of the Japan Institute of Metals, Vol. 17, No. 8 (1978), 662 shows that for duplex stainless steel containing 21 to 23% Cr, its ferrite phase fraction and material fracture in corrosive environments. The relationship with time is shown, and it can be read that the corrosion resistance is greatly impaired when the ferrite phase fraction is 20% or less, or 80% or more.
- the ferrite phase fraction of duplex stainless steel should be 35% or more and 65% or less based on the influence on corrosion resistance including the above. Since the material of the present invention is a two-phase stainless steel pipe used for applications requiring corrosion resistance, it is important to make it into an appropriate two-phase fraction state from the viewpoint of corrosion resistance. Therefore, the appropriate two-phase fraction state in the present invention is at least a ferrite phase fraction of 20% or more and 80% or less in the duplex stainless steel pipe structure. Further, when used in an environment where corrosion resistance is more strictly required, it is preferable to set the ferrite phase to 35 to 65% in accordance with ISO15156-3.
- a steel material having the above duplex stainless steel composition is prepared.
- Various melting processes can be applied to the melting of duplex stainless steel, and there is no limitation.
- a vacuum melting furnace or an atmospheric melting furnace can be used when manufacturing iron scrap or a mass of each element by electromelting.
- an Ar—O 2 mixed gas bottom blow decarburization furnace, a vacuum decarburization furnace, or the like can be used.
- the molten material is solidified by static casting or continuous casting to form an ingot or slab, which is then hot-rolled or forged into a round billet shape to form a steel material.
- Hot forming Piercing process
- any method such as a Mannesmann method or an extrusion pipe forming method can be used.
- an elongator, an assel mill, a mandrel mill, a plug mill, a sizer, a stretch reducer or the like, which is a hot rolling process for performing wall thickness reduction and outer diameter standardization on a hollow tube, may be used.
- the temperature of the duplex stainless steel during hot rolling gradually decreases from the high temperature state during heating during hot rolling.
- the corrosion resistant element may be consumed as a thermochemically stable precipitate in various temperature regions during the temperature decrease, and the corrosion resistance may decrease. Further, there is a possibility that a phase transformation to an embrittlement phase occurs and the low temperature toughness is remarkably reduced.
- duplex stainless steel withstands various corrosive environments, it is important that the austenite phase and ferrite phase fraction during use be in an appropriate two-phase state, but since the cooling rate from the heating temperature cannot be controlled, It becomes difficult to control the two-phase fraction that changes sequentially depending on the holding temperature. Due to the above problems, solid solution of precipitates in steel, reverse transformation of embrittlement phase to non-embrittlement phase, rapid cooling after heating at high temperature for the purpose of making the phase fraction into an appropriate two-phase state The solid solution heat treatment for performing is often used. By this treatment, precipitates and embrittlement phases are dissolved in the steel, and the phase fraction is controlled to an appropriate two-phase state.
- the temperature of the solid solution heat treatment is a high temperature of 1000°C or higher, although the temperature at which the precipitate dissolves, the reverse transformation of the embrittlement phase, and the two-phase state in which the phase fraction is appropriate differ depending on the added element.
- quenching is performed to maintain the solid solution state, but various refrigerants such as compressed air cooling, mist, oil, and water can be used.
- the seamless steel pipe contains an austenite phase with low yield strength, so the strength required for oil and gas well mining cannot be obtained as it is. Therefore, the strength of the pipe is enhanced by utilizing the dislocation strengthening by various processes.
- the strength grade of the duplex stainless seamless steel pipe after strengthening is determined by the tensile yield strength in the pipe axial direction.
- the strength of the pipe is strengthened by either (1) stretching in the axial direction of the pipe or (2) bending and bending back in the circumferential direction of the pipe. ..
- the nitride finely precipitated in the steel maintains the strength at high temperature even after the heat treatment, and the amount of solid solution N is controlled.
- coarse precipitation of the corrosion resistant elements Cr and Mo-based nitrides is suppressed, and deterioration in corrosion resistance performance and strength are suppressed. That is, it has a higher corrosion resistance than that containing no essential additive element, and it is possible to improve the decrease in the compressive yield strength in the pipe axis direction caused by the stretching process in the pipe axis direction while further increasing the strength.
- the effect of reducing the processing load by softening the material during processing is achieved in addition to the same effect as the heat treatment described above by performing the drawing processing with the drawing processing temperature in the tube axis direction set to 150-600°C excluding 460-480°C. Is obtained. Even if heat treatment after stretching and increasing the processing temperature are performed in combination with the addition of essential additive elements, the deterioration of the compressive yield strength in the pipe axis direction caused by the stretching process in the pipe axis direction is improved without affecting the corrosion resistance. can do.
- the heat treatment may be performed after the stretching process is performed at 150 to 600° C. excluding 460 to 480° C., and the heating temperature during the heat treatment is preferably 150 to 600° C. excluding 460 to 480° C. ..
- the upper limit of the processing temperature during stretching and the heating temperature during heat treatment must be a temperature at which dislocation strengthening due to processing does not disappear, and can be applied up to 600°C or lower. Also, processing at the embrittlement temperature of the ferrite phase, 460 to 480°C, should be avoided as it will lead to cracking during processing in addition to the deterioration of product properties due to embrittlement of the pipe.
- the temperature during heat treatment or the processing temperature during stretching is less than 150°C, it will be in the temperature range where a sudden decrease in yield strength occurs. Further, in order to obtain a sufficient processing load reducing effect, the temperature is set to 150°C or higher. The temperature is preferably 350 to 450° C. in order to avoid passing through the embrittlement phase during heating and cooling.
- the amount of strain is adjusted by repeating bending and bending back and changes in the amount of bending, but the applied strain is an additional shear strain that does not change the shape before and after working. Furthermore, since almost no strain is generated in the pipe axis direction and the dislocation is strengthened by the strain applied in the pipe circumferential direction and the pipe wall thickness direction, the Bausinger effect in the pipe axis direction can be suppressed. That is, since there is no or little decrease in the tube axis compressive strength as in cold drawing rolling or cold Pilger rolling, the degree of freedom in designing the screw fastening portion can be improved.
- the compressive strength in the circumferential direction of the pipe is improved, and it is possible to obtain a steel pipe that is strong against external pressure at the time of deep oil well/gas well mining. Bending and bending back in the pipe circumferential direction cannot give large changes in outer diameter and wall thickness as in cold drawing rolling or cold Pilger rolling, but especially in the pipe axial direction and pipe circumferential compression against pipe axial tension. This is effective when it is required to reduce the strength anisotropy in the direction.
- FIG. 1(a) and 1(b) are cross-sectional views when the tool contact portion is provided at two locations
- FIG. 1(c) is a cross-sectional view when the tool contact portion is provided at three locations.
- a thick arrow in FIG. 1 indicates a direction in which a force is applied when flattening a steel pipe.
- FIG. 1 when performing the second flattening process, move the tool to rotate the steel pipe or shift the tool position so that the tool comes into contact with the place where the first flattening process has not been performed. It may be devised such as swelling (the hatched portion in FIG. 1 indicates the first flat portion).
- bending and bending back in the circumferential direction of the pipe to flatten the steel pipe is performed intermittently or continuously over the entire circumferential direction of the pipe, so that the strain due to bending near the maximum value of the curvature of the steel pipe.
- strain due to bending back is applied toward the minimum value of the curvature of the steel pipe.
- the strain due to bending and bending back deformation necessary for improving the strength (dislocation strengthening) of the steel pipe is accumulated.
- this processing mode unlike the processing mode in which the wall thickness and outer diameter of the pipe are compressed, a large amount of power is not required and deformation due to flattening minimizes shape changes before and after processing. The feature is that it can be processed while staying.
- rolls may be used, and if the steel pipe is flattened and rotated between two or more rolls arranged in the circumferential direction of the steel pipe, it is easily repeatedly bent and bent back to cause deformation. It is possible to give strain. Further, if the rotation axis of the roll is inclined within 90° with respect to the rotation axis of the pipe, the steel pipe advances in the direction of the rotation axis of the pipe while undergoing flattening, so that continuous processing can be easily performed. Further, the continuous processing using this roll, for example, if the gap between the rolls is appropriately changed so that the flatness amount is changed with the progress of the steel pipe, the first and second steel pipes can be easily processed.
- the curvature (flatness) of can be changed. Therefore, it is possible to homogenize strain in the thickness direction by changing the movement path of the neutral line by changing the roll interval. Similarly, the same effect can be obtained by changing the flatness by changing the roll diameter instead of the roll interval. Also, these may be combined. Although the equipment becomes complicated, if the number of rolls is 3 or more, whirling of the pipe during processing can be suppressed, and stable processing becomes possible.
- the bending temperature may be normal temperature.
- the processing temperature is room temperature, all N can be in a solid solution state, which is preferable from the viewpoint of corrosion resistance.
- the addition of an essential additive element causes the cold processing load to be high and the processing temperature even when the processing is difficult. Is effective because the material can be softened by raising the temperature.
- the upper limit of processing temperature must be a temperature at which dislocation strengthening due to processing does not disappear, and it can be applied up to 600°C or lower. Also, processing at the embrittlement temperature of the ferrite phase, 460 to 480°C, should be avoided as it will lead to cracking during processing in addition to the deterioration of product properties due to embrittlement of the pipe.
- the processing temperature is preferably 600° C. or lower excluding 460 to 480° C. More preferably, the upper limit is 450° C. in order to save energy and to avoid passing through the embrittlement phase during heating and cooling. Further, the rise of the processing temperature also has the effect of slightly reducing the strength anisotropy of the pipe after processing, and is therefore effective when the strength anisotropy becomes a problem.
- the processing (1) or (2) used for strengthening dislocations further heat treatment may be performed in the present invention.
- the essential additive element is added so as to satisfy the formula (1), the strength is improved by the fine precipitates with the additive element, and the amount of solute N can be controlled, so that the corrosion resistance and strength are not reduced by heat treatment.
- the strength anisotropy can be improved while maintaining these.
- the heating temperature of the heat treatment is less than 150°C, the temperature range is in which the yield strength rapidly decreases, so the heating temperature is preferably 150°C or higher. Further, the upper limit of the heating temperature needs to be a temperature at which dislocation strengthening due to processing does not disappear, and it can be applied up to 600°C or lower.
- heat treatment at the embrittlement temperature of the ferritic phase should be avoided because it leads to deterioration of product properties due to embrittlement of the tube. Therefore, when further heat treatment is performed, it is preferable to perform heat treatment at a heating temperature of 150 to 600° C. excluding 460 to 480° C. It is more preferable to set the temperature to 350 to 450° C. in order to save energy and avoid passing through the embrittlement phase during heating and cooling while obtaining the effect of improving the anisotropy.
- the cooling rate after heating may be either air cooling or water cooling.
- the duplex stainless seamless steel pipe of the present invention can be obtained.
- the strength grade of duplex stainless seamless steel pipes for oil and gas wells is determined by the pipe axial tensile yield strength at which the highest load occurs, and in the duplex stainless seamless steel pipe of the present invention, the pipe axial tensile yield The strength is 757 MPa or more.
- the pipe axial tensile yield strength does not reach 757 MPa in the state of solid solution heat treatment.
- the tensile yield strength in the pipe axis direction is adjusted and used by the dislocation strengthening by the above-mentioned cold working (drawing work in the pipe axis direction or bending and bending back work in the pipe circumferential direction).
- the higher the tensile yield strength in the pipe axial direction the thinner the wall can be used to design a well design for mining, which is advantageous in terms of cost.
- the wall thickness is thinned without changing the outer diameter of the pipe, it becomes possible to increase the depth. It becomes weak against crushing due to external pressure and cannot be used.
- the tensile yield strength in the pipe axis direction is often used within a range of 1033.5 MPa at most.
- the ratio of the compressive yield strength in the pipe axis direction and the tensile yield strength in the pipe axis direction is 0.85 to 1.15.
- 0.85 to 1.15 it becomes possible to withstand a higher stress against the compressive stress in the axial direction of the pipe that occurs when the screw is fastened or when the steel pipe bends in the well, which is necessary for compressive stress resistance. It is possible to reduce the existing pipe wall thickness. Increasing the degree of freedom in pipe wall thickness, especially expanding the range of wall thinning, will lead to cost reductions due to material cost reductions and higher production volumes.
- the strength of the pipe is increased while maintaining corrosion resistance, and the pipe axial compressive yield strength/pipe axial tensile yield strength is further increased. It can be 0.85 to 1.15. Further, if the bending/bending back processing is performed warm or a low temperature heat treatment is further performed after each processing, the tube axial compressive yield strength/tube axial tensile yield strength can be made closer to 1 with less anisotropy. ..
- the ratio of the compressive yield strength in the pipe circumferential direction to the tensile yield strength in the pipe axial direction is 0.85 or more.
- the depth of minable well depends on the tensile stress in the pipe axial direction when the wall thickness is the same. In order not to be crushed by the external pressure generated in a deep well, it is preferable that the compressive yield strength in the pipe circumferential direction is 0.85 or more against the tensile yield stress in the pipe axial direction.
- the aspect ratio of the austenite grains divided by the crystal orientation angle difference of 15° or more in the wall thickness direction in the tube axis direction is 9 or less.
- the austenite grains having an aspect ratio of 9 or less are preferably 50% or more in area fraction.
- the duplex stainless steel of the present invention is adjusted to an appropriate ferrite phase fraction by the solution heat treatment temperature.
- a structure having a plurality of crystal grains separated by an azimuth angle of 15° or more by recrystallization during hot working or heat treatment is formed.
- the austenite grains have a small aspect ratio.
- the duplex stainless steel pipe in this state does not have the axial tensile yield strength required for oil country tubular goods, but the axial compressive yield strength/axial tensile yield strength of the tubular tube is also close to 1. .. Then, in order to obtain the tensile yield strength in the pipe axial direction required for the oil country tubular goods, (1) drawing processing in the pipe axial direction: cold drawing rolling, cold Pilger rolling, and (2) bending bending in the pipe circumferential direction. Back processing is performed. These processings cause changes in the tube axial compressive yield strength/tube axial tensile yield strength and the aspect ratio of the austenite grains.
- the aspect ratio of the austenite grains and the tube axial compressive yield strength/tube axial tensile yield strength are closely related. Specifically, in the processing of (1) or (2), the yield strength is improved in the direction in which the austenite grains in the thick section in the axial direction of the pipe are stretched before and after processing, but instead, in the opposite direction, due to the Bausinger effect. Yield strength decreases, and the value of compressive yield strength in tube axial direction/tensile yield strength in tube axial direction decreases. From this, by controlling the aspect ratio of the austenite grains before and after working in (1) or (2) to be small, it is possible to obtain a steel pipe with little strength anisotropy in the pipe axis direction.
- the aspect ratio of the austenite phase is 9 or less, a stable steel pipe with little strength anisotropy can be obtained. Further, if the austenite grains having an aspect ratio of 9 or less have an area fraction of 50% or more, it is possible to obtain a stable steel pipe having little strength anisotropy. By setting the aspect ratio to 5 or less, a steel pipe with less strength anisotropy can be obtained more stably. The smaller the aspect ratio, the more the strength anisotropy can be reduced. Therefore, the lower limit is not particularly limited, and the closer to 1, the better.
- the aspect ratio of the austenite grains for example, by observing the crystal orientation angle 15 ° or more of the austenite phase by the crystal orientation analysis of the tube axial direction thick section, the long side when the grains are placed in a rectangular frame. And the ratio of the short sides. Since austenite grains having a small grain size have a large measurement error, when the austenite grains having a small grain size are included, an error may occur in the aspect ratio. Therefore, the austenite grains for measuring the aspect ratio are preferably 10 ⁇ m or more in diameter when a perfect circle having the same area is drawn by using the measured grain area.
- the processing of (1) or (2) it is necessary not to stretch in the pipe axis direction and further reduce the wall thickness. It is valid.
- the processing method of (1) in principle, since the tube axial direction stretching and the wall thickness reduction are involved, the aspect ratio becomes larger than that before the processing, and the strength anisotropy is likely to occur. For this reason, the processing amount should be reduced (the thickness reduction should be 40% or less, or the stretching in the pipe axial direction should be 50% or less to suppress the stretching of the structure), and the reduction of the stretching thickness and the outer circumference of the pipe at the same time.
- the processing method (2) is bending and bending back deformation in the pipe circumferential direction, basically the aspect ratio does not change. Therefore, the processing method of (2) is very effective in keeping the aspect ratio small and reducing the strength anisotropy, although there is a limit in the amount of shape change such as stretching and wall thinning of the pipe.
- the austenite grains having an aspect ratio of 9 or less are increased to 50% or more in area fraction. Can be controlled.
- the aspect ratio does not change even if heat treatment is performed after processing.
- the ferrite phase preferably has a small aspect ratio for the same reason as the austenite phase, but the austenite phase has a lower yield strength and tends to affect the Bauschinger effect after processing.
- the round billet was inserted again into the heating furnace and held at a high temperature of 1200°C or higher, and then hot formed into a seamless bare tube with an outer diameter of ⁇ 70 mm and an inner diameter of 58 mm (wall thickness 6 mm) using a Mannesmann piercing and rolling machine. did.
- the individual pipes of each component were subjected to solid solution heat treatment at a temperature at which the ferrite and austenite fractions were in an appropriate two-phase state, and were processed for strengthening.
- Table 3 as the processing method, two kinds of drawing processing, which is one of the drawing processing in the tube axis direction, and bending and bending back processing were performed. After the drawing rolling or bending and bending back work, a part was cut out and the structure was observed, and it was confirmed that the ferrite phase and the austenite phase had an appropriate fraction.
- the crystal orientation analysis by EBSD was performed in the wall thickness direction of the pipe cross section parallel to the pipe axis direction, and the aspect ratio of the austenite grains divided by the crystal orientation angle of 15° was measured.
- the measurement area was 1.2 mm ⁇ 1.2 mm, and the aspect ratio was measured for austenite grains with a grain size of 10 ⁇ m or more assuming a perfect circle.
- the thickness reduction was performed in the range of 3 to 20% and the outer peripheral length was reduced by 3 to 20%.
- a rolling mill in which three cylindrical rolls are arranged on the outer circumference of the pipe at a pitch of 120° (Fig. 1(c)), and the pipe spacing is made 10 to 15% smaller than the pipe outer diameter. It was performed by sandwiching the outer circumference and rotating the tube.
- warm processing at 150 to 550°C was performed under some conditions. After the cold and warm working, a heat treatment at 150 to 550° C. was performed as a low temperature heat treatment under some conditions.
- Steel pipes obtained by cold and warm working and low temperature heat treatment are tensile grades in the longitudinal direction of the pipe axis, compressive yield strength and circumferential compressive yield strength, and are the strength grade of steel pipes for oil and gas wells.
- Axial tensile yield strength and pipe axial compressive yield strength/pipe axial tensile yield strength and pipe circumferential compressive yield strength/pipe axial tensile yield strength were measured.
- a stress corrosion test was conducted in a chloride and sulfide environment.
- the corrosive environment was adjusted to pH 3.0 by adding H 2 S gas at a pressure of 0.01 to 0.10 MPa to an aqueous solution simulating an oil well during mining (20% NaCl + 0.5% CH 3 COOH + CH 3 COONa aqueous solution). 25°C).
- H 2 S gas at a pressure of 0.01 to 0.10 MPa to an aqueous solution simulating an oil well during mining (20% NaCl + 0.5% CH 3 COOH + CH 3 COONa aqueous solution). 25°C).
- a 4-point bending test piece having a wall thickness of 5 mm was cut out so that the stress could be applied in the longitudinal direction of the pipe axis, and 90% of the stress was applied to the tensile yield strength in the pipe axis direction and immersed in a corrosive water solution.
- Corrosion was evaluated by immersing it in a corrosive aqueous solution for 720 hours under stress, and then taking it out immediately after the stress-applied surface had no cracks (no cracks), and when cracks were observed, x (cracks). Yes).
- Table 3 shows the manufacturing conditions and evaluation results.
- the processing method, the number of times of processing (pass), and the processing temperature described here indicate processing for further obtaining strength after heat-treating the steel pipe after hot rolling, and specifically, drawing rolling and bending/bending back processing. Refers to.
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Abstract
Description
0.150>N-(1.58Ti+2.70Al+1.58V+1.44Nb)・・・(1)
ここで、N、Ti、Al、V、Nbは各元素の含有量(質量%)である。(但し、含有しない場合は0(零)%とする。)
本発明は以上の知見に基づきなされたものであり、その要旨は次のとおりである。
[1]質量%で、C:0.005~0.08%、Si:0.01~1.0%、Mn:0.01~10.0%、Cr:20~35%、Ni:1~15%、Mo:0.5~6.0%、N: 0.150~0.400%未満を含有し、さらにTi:0.0001~0.3%、Al:0.0001~0.3%、V:0.005~1.5%、Nb:0.005~1.5%未満のうちから選ばれた1種または2種以上を含有し、残部がFeおよび不可避的不純物からなる成分組成であり、かつN、Ti、Al、V、Nbが、下記式(1)を満たすように含有し、管軸方向引張降伏強度が757MPa以上であり、管軸方向圧縮降伏強度/管軸方向引張降伏強度が0.85~1.15である二相ステンレス継目無鋼管。
0.150>N-(1.58Ti+2.70Al+1.58V+1.44Nb)・・・(1)
ここで、N、Ti、Al、V、Nbは各元素の含有量(質量%)である。(但し、含有しない場合は0(零)%とする。)
[2]管周方向圧縮降伏強度/管軸方向引張降伏強度が0.85以上である[1]に記載の二相ステンレス継目無鋼管。
[3]さらに質量%で、W:0.1~6.0%、Cu:0.1~4.0%のうちから選ばれた1種または2種を含有する[1]または[2]に記載の二相ステンレス継目無鋼管。
[4]さらに質量%で、B:0.0001~0.010%、Zr:0.0001~0.010%、Ca:0.0001~0.010%、Ta:0.0001~0.3%、REM:0.0001~0.010%のうちから選ばれた1種または2種以上を含有する[1]~[3]のいずれかに記載の二相ステンレス継目無鋼管。
[5][1]~[4]のいずれかに記載の二相ステンレス継目無鋼管の製造方法であって、管軸方向への延伸加工を行い、その後、460~480℃を除く150~600℃の加熱温度で熱処理する二相ステンレス継目無鋼管の製造方法。
[6][1]~[4]のいずれかに記載の二相ステンレス継目無鋼管の製造方法であって、460~480℃を除く150~600℃の加工温度で管軸方向への延伸加工を行う二相ステンレス継目無鋼管の製造方法。
[7]前記延伸加工後、さらに、460~480℃を除く150~600℃の加熱温度で熱処理する[6]に記載の二相ステンレス継目無鋼管の製造方法。
[8][1]~[4]のいずれかに記載の二相ステンレス継目無鋼管の製造方法であって、管周方向の曲げ曲げ戻し加工を行う二相ステンレス継目無鋼管の製造方法。
[9]前記管周方向の曲げ曲げ戻し加工の加工温度は、460~480℃を除く600℃以下である[8]に記載の二相ステンレス継目無鋼管の製造方法。
[10]前記曲げ曲げ戻し加工後、さらに、460~480℃を除く150~600℃の加熱温度で熱処理する[8]または[9]に記載の二相ステンレス継目無鋼管の製造方法。
Cはオーステナイト相形成元素であり、適量の含有で相分率の適正化に役立つ。しかし、過剰な含有は炭化物の形成により耐食性の低下を招く。そのため、Cの上限は0.08%とする。下限については、C量低下に伴うオーステナイト相の低下を、その他オーステナイト相形成元素で賄うことができるため特に設ける必要はないが、C量が低すぎると溶解時の脱炭コストが上昇するため、0.005%以上とする。
Siは鋼の脱酸作用があるため、溶鋼中への適量の含有が有効である。しかし、多量のSi含有に伴う鋼中への残存は、加工性と低温靱性を損なう。そのため、Siの上限は1.0%とする。下限については、脱酸後のSiを過剰に低減することは製造コスト上昇につながるため、0.01%以上とする。なお、十分に脱酸作用を得つつ、過剰に鋼中に残存することによる副作用抑制を両立する観点から、Siは0.2~0.8%とすることが好ましい。
Mnは強力なオーステナイト相形成元素であり、かつその他のオーステナイト相形成元素に比べ安価である。さらに低温熱処理を実施してもCやNのように耐食性元素を消費することがない。そのため、CやNを低減した際に二相ステンレス継目無鋼管のオーステナイト相分率を適切な2相状態とするために、0.01%以上含有する必要がある。一方で、Mnの過剰な含有は低温靱性を低下させる。そのため、10.0%以下とする。低温靭性を損なわないためには1.0%未満であることが好ましい。一方で、低温靱性に注意しつつ、コスト低減を両立させる観点でMnをオーステナイト相形成元素として十分に活用したい場合は2.0~8.0%が好適である。下限については、溶鋼中に混入する不純物元素であるSの無害化にMnが有効であり、微量添加で鋼の耐食性、靭性を大きく劣化させるSをMnSとして固定する効果があるため、Mnは0.01%以上含有する。
Crは鋼の不動態被膜を強固にし、耐食性能を高めるもっとも重要な元素である。過酷な腐食環境で利用される二相ステンレス継目無鋼管には20%以上のCr量が必要となる。Cr量が増加するほど耐食性向上に寄与するが、35%超えの含有は溶解から凝固する過程で脆化相が析出し全体に割れが発生してしまい、その後の成形加工が困難になる。そのため上限は35%とする。なお、耐食性の確保と製造性の両立の観点から好ましい範囲は22~28%である。
Niは強力なオーステナイト相形成元素であり、かつ鋼の低温靱性を向上させる。そのため安価なオーステナイト相形成元素であるMnの利用では低温靱性が問題になる場合に積極的に活用すべきであり、下限は1%とする。一方で、Niはその他オーステナイト相形成元素中で最も高価な元素であり、含有量の増加は製造コスト上昇につながる。そのため、不要に多く含有することは好ましくない。そのため、上限は15%とする。なお、低温靱性が問題にならない用途の場合は1~5%の範囲で、その他元素と複合添加することが好ましい。一方で、高い低温靱性が必要な場合はNiの積極的な添加が有効であり、5~13%の範囲とすることが好ましい。
Moは含有量に応じて鋼の耐孔食性を高める。そのため腐食環境に応じて適量添加される。一方で過剰なMoの含有は溶鋼~凝固時に脆化相が析出し、凝固組織中に多量の割れを発生させ、その後の成形安定性を大きく損なう。そのため、上限は6.0%とする。Moの含有は含有量に応じて耐孔食性を向上させるが、硫化物環境で安定した耐食性を維持するためには0.5%以上が必要である。なお、二相ステンレス継目無鋼管に必要とされる耐食性と製造安定性両立の観点から1.0~5.0%が好適な範囲となる。
Nは強力なオーステナイト相形成元素であり、かつ安価である。また、鋼中に固溶していれば耐食性能と強度向上に有用な元素であるため積極的に利用される。しかし、N自体は安価であるが、過大なN添加は特殊な設備と添加時間が必要となり、製造コストの増加につながるため、上限は0.400%未満とする。一方でNの下限は0.150%以上とするべきである。本発明ではTi、Al、V、Nbのいずれか、または複合添加することを必須とし、凝固後の冷却の過程でこれらの添加物を微細に窒化物として形成させることで強度向上効果を得る。N量が少なすぎると安定した強度向上効果が得られにくくなるため、下限を0.150%以上とすることが必要となる。さらに、十分な強度向上効果を得るためのより好ましい範囲は0.155~0.320%の範囲である。
Ti、Al、V、Nbは適量の含有で溶解からの冷却中に微細な窒化物を生成し強度を向上させるとともに、鋼中の固溶するN量を適切に制御することが可能になる。これにより、CrやMoなどの耐食性元素が窒化物として消費、かつ粗大に析出することで、耐食性能と強度が低下する現象を抑制することができる。この効果を得るための含有量の下限は、Ti:0.0001%、Al:0.0001%、V:0.005%、Nb:0.005%以上である。また、過剰な添加はコストの上昇や熱間での成形性の悪化につながるため、それぞれTi:0.3%以下、Al:0.3%以下、V:1.5%以下、Nb:1.5%未満とする。
0.150>N-(1.58Ti+2.70Al+1.58V+1.44Nb)・・・(1)
ここで、N、Ti、Al、V、Nbは各元素の含有量(質量%)である。(但し、含有しない場合は0(零)%とする。)
安定した耐食性能と高強度は下記式(1)を満たすことで達成できる。すなわち、本発明によるTi、Al、V、Nbの含有量は鋼中に添加したN量に対して最適な量であるべきであり、N量に対し含有量が少ない場合はNの固定と微細析出を十分にできずに耐食性能や強度が安定しない。式(1)はTi、Al、V、Nbを単独、複合含有する場合について、含有されるN量に対して最適化を行える式になっており、安定した耐食性能と強度を得ることが可能になる。
W:0.1~6.0%
WはMoと同様に含有量に応じて耐孔食性を高めるが、過剰に含有すると熱間加工時の加工性を損ない製造安定性を損なう。そのため、Wを含有する場合は、上限は6.0%とする。Wの含有は含有量に応じて耐孔食性を向上させるため、特に下限を設ける必要はないが、二相ステンレス継目無鋼管の耐食性能を安定させる理由で0.1%以上の含有が好適である。なお、二相ステンレス継目無鋼管に必要とされる耐食性と製造安定性の観点から1.0~5.0%がより好適な範囲となる。
Cuは強力なオーステナイト相形成元素であり、かつ鋼の耐食性を向上させる。そのためその他オーステナイト相形成元素であるMnやNiでは耐食性が不足する場合に積極的に活用すべきである。一方で、Cuは含有量が多くなりすぎると熱間加工性の低下を招き、成形が困難になる。そのため、含有する場合、Cuは4.0%以下とする。含有量の下限は特に規定する必要はないが、0.1%以上の含有で耐食性効果が得られる。なお、耐食性の向上と熱間加工性の両立の観点から1.0~3.0%の添加量がより好適な範囲である。
B、Zr、Ca、REMは、ごく微量を添加すると粒界の結合力向上や、表面の酸化物の形態を変化させ熱間の加工性、成形性を向上する。二相ステンレス継目無鋼管は一般的に難加工材料であるため、加工量や加工形態に起因した圧延疵や形状不良が発生しやすいが、そのような問題が発生するような成形条件の場合にこれらの元素は有効である。添加量は下限を特に設ける必要はないが、含有する場合は0.0001%以上により加工性や成形性向上の効果が得られる。一方で、添加量が多くなりすぎると逆に熱間加工性を悪化させることに加え、希少元素のため合金コストが増大する。そのため添加量の上限は、B、Zr、Ca、REMについてはそれぞれ0.010%とする。Taは少量添加すると脆化相への変態を抑制し、熱間加工性と耐食性を同時に向上する。したがって、Taを含有する場合は0.0001%以上とする。熱間加工やその後の冷却で脆化相が安定な温度域で長時間滞留する場合にこれらの元素は有効である。一方で添加量が多くなりすぎると合金コストが増大するため、Taを含有する場合は上限を0.3%とする。
管の冷間圧延法で油井・ガス井採掘に関して規格化されているのは冷間引抜圧延、冷間ピルガー圧延の2種類であり、いずれの手法も管軸方向への高強度化が可能であり、適宜利用できる。これらの手法では、主に圧下率と外径変化率を変化させて必要な強度グレードまで高強度化を行う。一方で、冷間引抜圧延や冷間ピルガー圧延加工は管の外径と肉厚を減じ、その分を管軸長手方向に大きく延伸する圧延形態であるため、管軸長手方向へは高強度化が容易に起こる。その反面、管軸圧縮方向へ大きなバウシンガー効果が発生し、管軸方向圧縮降伏強度が管軸引張降伏強度に対し最大20%程度低下することが問題として知られている。
油井・ガス井採掘用二相ステンレス継目無鋼管の冷間加工手法として規格化されていないが、管周方向への曲げ曲げ戻し加工による転位強化を利用した管の高強度化も利用できる。図面に基づいて、本加工手法について説明する。この手法は、圧延によるひずみが管軸長手方向へ生じる冷間引抜圧延や冷間ピルガー圧延加工と異なり、図1に示すように、ひずみは管の扁平による曲げ加工後(1回目の扁平加工)、再び真円に戻す際の曲げ戻し加工(2回目の扁平加工)により与えられる。この手法では、曲げ曲げ戻しの繰り返しや曲げ量の変化を利用してひずみ量を調整するが、与えるひずみは加工前後の形状を変えることがない付加的せん断ひずみである。さらに、管軸方向へのひずみがほとんど発生せず管周方向と管肉厚方向へ与えられたひずみによる転位強化で高強度化するため、管軸方向へのバウシンガー効果を抑制できる。つまり、冷間引抜圧延や冷間ピルガー圧延のように管軸圧縮強度の低下がない、または少ないため、ネジ締結部の設計自由度が向上できる。さらに、管外周長が減ずるように加工を行えば、管周方向圧縮強度が向上し、高深度の油井・ガス井採掘時の外圧に対しても強い鋼管とすることができる。管周方向への曲げ曲げ戻し加工は、冷間引抜圧延や冷間ピルガー圧延のように大きな外径、肉厚変化を与えることはできないが、特に管軸方向と管軸引張に対する管周方向圧縮方向の強度異方性の低減が求められる場合に有効である。
Claims (10)
- 質量%で、C:0.005~0.08%、
Si:0.01~1.0%、
Mn:0.01~10.0%、
Cr:20~35%、
Ni:1~15%、
Mo:0.5~6.0%、
N: 0.150~0.400%未満を含有し、さらに
Ti:0.0001~0.3%、
Al:0.0001~0.3%、
V:0.005~1.5%、Nb:0.005~1.5%未満のうちから選ばれた1種または2種以上を含有し、残部がFeおよび不可避的不純物からなる成分組成であり、かつN、Ti、Al、V、Nbが、下記式(1)を満たすように含有し、管軸方向引張降伏強度が757MPa以上であり、管軸方向圧縮降伏強度/管軸方向引張降伏強度が0.85~1.15である二相ステンレス継目無鋼管。
0.150>N-(1.58Ti+2.70Al+1.58V+1.44Nb)・・・(1)
ここで、N、Ti、Al、V、Nbは各元素の含有量(質量%)である。(但し、含有しない場合は0(零)%とする。) - 管周方向圧縮降伏強度/管軸方向引張降伏強度が0.85以上である請求項1に記載の二相ステンレス継目無鋼管。
- さらに質量%で、W:0.1~6.0%、
Cu:0.1~4.0%のうちから選ばれた1種または2種を含有する請求項1または2に記載の二相ステンレス継目無鋼管。 - さらに質量%で、B:0.0001~0.010%、
Zr:0.0001~0.010%、
Ca:0.0001~0.010%、
Ta:0.0001~0.3%、
REM:0.0001~0.010%のうちから選ばれた1種または2種以上を含有する請求項1~3のいずれかに記載の二相ステンレス継目無鋼管。 - 請求項1~4のいずれかに記載の二相ステンレス継目無鋼管の製造方法であって、管軸方向への延伸加工を行い、その後、460~480℃を除く150~600℃の加熱温度で熱処理する二相ステンレス継目無鋼管の製造方法。
- 請求項1~4のいずれかに記載の二相ステンレス継目無鋼管の製造方法であって、460~480℃を除く150~600℃の加工温度で管軸方向への延伸加工を行う二相ステンレス継目無鋼管の製造方法。
- 前記延伸加工後、さらに、460~480℃を除く150~600℃の加熱温度で熱処理する請求項6に記載の二相ステンレス継目無鋼管の製造方法。
- 請求項1~4のいずれかに記載の二相ステンレス継目無鋼管の製造方法であって、管周方向の曲げ曲げ戻し加工を行う二相ステンレス継目無鋼管の製造方法。
- 前記管周方向の曲げ曲げ戻し加工の加工温度は、460~480℃を除く600℃以下である請求項8に記載の二相ステンレス継目無鋼管の製造方法。
- 前記曲げ曲げ戻し加工後、さらに、460~480℃を除く150~600℃の加熱温度で熱処理する請求項8または9に記載の二相ステンレス継目無鋼管の製造方法。
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2019
- 2019-11-01 US US17/296,626 patent/US20220018007A1/en active Pending
- 2019-11-01 EP EP19890675.2A patent/EP3854890A4/en active Pending
- 2019-11-01 BR BR112021010023-7A patent/BR112021010023A2/pt not_active Application Discontinuation
- 2019-11-01 AU AU2019389490A patent/AU2019389490B2/en active Active
- 2019-11-01 WO PCT/JP2019/042969 patent/WO2020110597A1/ja active Application Filing
- 2019-11-01 MX MX2021006279A patent/MX2021006279A/es unknown
- 2019-11-01 CA CA3118704A patent/CA3118704C/en active Active
- 2019-11-01 JP JP2020510630A patent/JP6756418B1/ja active Active
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Patent Citations (3)
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JPS55324B1 (ja) | 1968-02-29 | 1980-01-07 | ||
JP2009007638A (ja) * | 2007-06-28 | 2009-01-15 | Nippon Yakin Kogyo Co Ltd | 二相ステンレス鋼およびその製造方法 |
WO2017086169A1 (ja) * | 2015-11-17 | 2017-05-26 | 株式会社神戸製鋼所 | 二相ステンレス鋼材および二相ステンレス鋼管 |
Non-Patent Citations (2)
Title |
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"The Japan Institute of Metals and Materials Newsletter", TECHNICAL DATA, vol. 17, no. 8, 1978 |
See also references of EP3854890A4 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2021157251A1 (ja) * | 2020-02-05 | 2021-08-12 | Jfeスチール株式会社 | ステンレス継目無鋼管およびその製造方法 |
JP6954492B1 (ja) * | 2020-02-05 | 2021-10-27 | Jfeスチール株式会社 | ステンレス継目無鋼管およびその製造方法 |
WO2021171836A1 (ja) * | 2020-02-27 | 2021-09-02 | Jfeスチール株式会社 | ステンレス鋼管およびその製造方法 |
WO2021256128A1 (ja) * | 2020-06-19 | 2021-12-23 | Jfeスチール株式会社 | 合金管およびその製造方法 |
JPWO2021256128A1 (ja) * | 2020-06-19 | 2021-12-23 | ||
JP7095811B2 (ja) | 2020-06-19 | 2022-07-05 | Jfeスチール株式会社 | 合金管およびその製造方法 |
EP4137243A4 (en) * | 2020-06-19 | 2023-07-05 | JFE Steel Corporation | ALLOY PIPE AND METHOD OF MANUFACTURE THEREOF |
CN115198182A (zh) * | 2022-06-30 | 2022-10-18 | 江西宝顺昌特种合金制造有限公司 | 一种含Ti的双相不锈钢及其制造方法 |
CN115198182B (zh) * | 2022-06-30 | 2023-08-18 | 江西宝顺昌特种合金制造有限公司 | 一种含Ti的双相不锈钢及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
JP6756418B1 (ja) | 2020-09-16 |
JPWO2020110597A1 (ja) | 2021-02-15 |
AU2019389490A1 (en) | 2021-05-27 |
CA3118704A1 (en) | 2020-06-04 |
EP3854890A1 (en) | 2021-07-28 |
CA3118704C (en) | 2023-05-16 |
MX2021006279A (es) | 2021-07-06 |
EP3854890A4 (en) | 2022-01-26 |
BR112021010023A2 (pt) | 2021-08-17 |
AU2019389490B2 (en) | 2022-06-23 |
US20220018007A1 (en) | 2022-01-20 |
AR117212A1 (es) | 2021-07-21 |
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