CN105283572A - Seamless steel pipe for line pipe used in sour environment - Google Patents

Seamless steel pipe for line pipe used in sour environment Download PDF

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Publication number
CN105283572A
CN105283572A CN201480031110.2A CN201480031110A CN105283572A CN 105283572 A CN105283572 A CN 105283572A CN 201480031110 A CN201480031110 A CN 201480031110A CN 105283572 A CN105283572 A CN 105283572A
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steel tube
content
weldless steel
steel
weldless
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CN105283572B (en
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小林宪司
荒井勇次
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Nippon Steel Corp
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Nippon Steel Corp
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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
    • 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
    • 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
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    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • 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
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C22C38/18—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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    • 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
    • C22C38/18—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
    • 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
    • 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
    • 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
    • C21D2211/009—Pearlite

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Abstract

Provided is a seamless steel pipe that is for use in a line pipe that is used in a sour environment, that does not require hardening or tempering to be performed, and that makes it possible to minimize the occurrence of blisters. A seamless steel pipe according to an embodiment of the present invention is provided with: a chemical composition comprising, in mass%, 0.08-0.24% of C, 0.10-0.50% of Si, 0.3-2.5% of Mn, 0.02% or less of P, 0.006% or less of S, 0.02-0.12% of Nb, 0.005-0.100% of Al, 0.0003-0.0050% of Ca, 0.0100% or less of N, 0.0050% or less of O, 0-0.1% of Ti, 0-0.03% of V, 0-0.6% of Cr, 0-0.3% of Mo, 0-0.4% of Ni, 0-0.3% of Cu, 0-0.005% of B, and a remainder of Fe and unavoidable impurities; and a structure comprising ferrite and pyrite. The seamless steel pipe has a yield strength of 350 or more and less than 450 MPa.

Description

The line-pipes weldless steel tube used under acid environment
Technical field
The present invention relates to weldless steel tube.Preferably relate to further and containing the hydrogen sulfide (H as corrosive gases 2s) the line-pipes weldless steel tube used under acid environment.
Background technology
Crude oil, Sweet natural gas contain hydrogen sulfide and moisture.This moistening hydrogen-sulfide environmental is called acid environment.Line pipe is used by the crude oil of oil well, gas well liquid loading, the pipeline of Sweet natural gas as conveyance.Therefore, line pipe uses under acid environment.For the line pipe used under acid environment, due to containing the saprophage under the environment of hydrogen sulfide, the hydrogen embrittlement of the hydrogen invaded in steel of resulting from becomes problem.
The SSC that hydrogen embrittlement results from steel under having static external stress and there is no external stress state under result from the hydrogen induced cracking (HydrogenInducedCracking: hereinafter referred to as HIC) of steel inside.For line pipe, most HIC becomes problem.Therefore, for line-pipes steel pipe, particularly HIC-resistance is required.
Line-pipes steel pipe has Welded Steel Pipe and weldless steel tube.Welded Steel Pipe has at welding seam part (weld part) that is axial or that spirally extend.The center segregation portion that the steel plate used in Welded Steel Pipe generates when thickness of slab central authorities have continuous casting, this center segregation portion has high HIC susceptibility.Therefore, particularly require that the line-pipes steel pipe of HIC-resistance preferably uses weldless steel tube.
The intensity of usual known steel is higher, more easily produces HIC.No. 2005/075694th, International Publication (patent documentation 1) proposes has high strength and the weldless steel tube of HIC-resistance excellence.
Specifically, line-pipes steel disclosed in patent documentation 1, composition is by mass% containing C:0.03 ~ 0.15%, Si:0.05 ~ 1.0%, Mn:0.5 ~ 1.8%, below P:0.015%, below S:0.04%, below O:0.01%, below N:0.007%, sol.Al:0.01 ~ 0.1%, below Ti:0.024%, Ca:0.0003 ~ 0.02%, and remainder is made up of Fe and impurity.In above-mentioned line-pipes steel, and then the size of TiN in steel is less than 30 μm.Describe in patent documentation 1 because TiN is fine, therefore can obtain excellent HIC-resistance.
Prior art document
Patent documentation
Patent documentation 1: No. 2005/075694th, International Publication
Patent documentation 2: Japanese Unexamined Patent Publication 2002-60893 publication
Patent documentation 3: No. 2011/152240th, International Publication
When manufacturing high strength seamless steel pipe, usually after hot procedure, implement quenching and temper, improve the intensity of weldless steel tube.On the other hand, also need without the need to high strength, yield strength is less than the low intensive line-pipes weldless steel tube of 450MPa.For this low intensive weldless steel tube, quenching and temper are not implemented and are omitted usually.
, thought as mentioned above in the past, if intensity is low, not easily produced HIC.But, the result new discovery of the investigation such as present inventor, when not only intensity is high, and the situation that intensity is low, also likely produce much as a kind of bubble (blister) and the small internal fissure of HIC.
Bubble refer to result from steel near surface, axially extended expansion at steel.In HIC-resistance test (NACETM0284 etc.) specified by NACE, illustrate and the high strength seamless steel pipe of excellent HIC-resistance also likely confirm the generation of bubble.But when HIC (bubble) is limited to the crackle of near surface, can not cause the leakage etc. of carried fluid, therefore for high strength seamless steel pipe in the past, bubble is not special problem.
But, for low intensive weldless steel tube, when load tensile stress, the multiple bubble in steel and small internal fissure are likely connected in the wall thickness direction of weldless steel tube and produce stress guide to hydrogen induced cracking (SOHIC, StressOrientedHydrogenInducedCracking).
Therefore, for not implementing the low intensive weldless steel tube of quenching and tempering, the generation of bubble and small internal fissure is preferably suppressed.In low strength steel, small internal fissure produces due to the reason same with bubble phase, is therefore conceived to bubble, suppresses it to produce.
Summary of the invention
The object of the invention is to, provide do not implement quenching and tempering, and for use under acid environment line pipe purposes when, the weldless steel tube of the generation of bubble and small internal fissure can be suppressed.
The weldless steel tube of present embodiment is the line pipe purposes used under acid environment.Above-mentioned weldless steel tube, it possesses following chemical constitution: by mass%, containing C:0.08 ~ 0.24%, Si:0.10 ~ 0.50%, Mn:0.3 ~ 2.5%, below P:0.02%, below S:0.006%, Nb:0.02 ~ 0.12%, Al:0.005 ~ 0.100%, Ca:0.0003 ~ 0.0050%, below N:0.0100%, below O:0.0050%, Ti:0 ~ 0.1%, V:0 ~ 0.03%, Cr:0 ~ 0.6%, Mo:0 ~ 0.3%, Ni:0 ~ 0.4%, Cu:0 ~ 0.3% and B:0 ~ 0.005%, remainder is made up of Fe and impurity, and described weldless steel tube possesses the tissue be made up of ferrite and pearlite, have 350 ~ less than the yield strength of 450MPa.
The weldless steel tube of present embodiment, does not implement Q-tempering, even if low strength, also can suppress the generation of bubble and small internal fissure.
Accompanying drawing explanation
Fig. 1 is the yield strength representing weldless steel tube and the bubble number (individual/20cm produced 2) the figure of relation.
Fig. 2 is the photograph image on two surfaces (being equivalent to outside surface and the internal surface of weldless steel tube) of corrosion test sheet after the bubble number determination test of example of the present invention (steel A4, wall thickness 20mm) in embodiment.
Fig. 3 is the photograph image on two surfaces (being equivalent to outside surface and the internal surface of weldless steel tube) of corrosion test sheet after the bubble number determination test of comparative example (steel B3, wall thickness 20mm) in embodiment.
Embodiment
Referring to accompanying drawing, embodiments of the present invention are described in detail.
The present inventor etc. carry out investigating and studying for the generation of the bubble do not implemented in the low intensive weldless steel tube of quenching and tempering, obtain following discovery.
Bubble produces due to following mechanism.Aggregation hydrogen around inclusion in steel, forms the starting point of hydrogen blistering (bubble).If the hydrogen pressure due to starting point raises steel surrender, generate be full of cracks.If generate be full of cracks, at the be full of cracks further aggregation dislocation in front end and hydrogen, be full of cracks progress.Generate bubble thus.
Do not implement in the low intensive weldless steel tube of quenching and tempering, the ferritic ratio that yield strength is low is many.Therefore think that ferrite is surrendered and produces bubble.Therefore, in order to suppress the generation of bubble, the intensity being improved steel by reinforced ferrite self or the pearlitic ratio etc. improved in steel is effective.
Fig. 1 is the yield strength representing weldless steel tube and the bubble number (individual/20cm produced 2) the figure of relation.Fig. 1 is obtained by following method.Manufacture the weldless steel tube with various chemical constitution.Now, cool by the weldless steel tube naturally cooling after hot-work or with the speed of cooling less than 5 DEG C/s, do not implement quenching and temper.
To manufactured each weldless steel tube, implement yield strength described later test, obtain yield strength.And then, implement bubble number determination test described later, obtain the bubble number (individual/20cm produced in each weldless steel tube 2), make Fig. 1.
With reference to Fig. 1, for weldless steel tube, till yield strength is 350MPa, along with yield strength raises, and bubble number significantly reduces.On the other hand, when yield strength is more than 350MPa, even if yield strength increases, bubble number does not also so change.
In a word, the curve of Fig. 1 has flex point near yield strength 350MPa.Therefore, if yield strength is more than 350MPa, can bubble number be suppressed low.
If improve C content, the perlite ratio in steel improves, and the yield strength of steel improves.But if C content improves, weldability reduces.Boxing is carried out at the scene that line-pipes weldless steel tube is arranging line pipe.If C content improves, the toughness of the connector portions of boxing reduces, and easily produces SSC (SSC).Therefore, be difficult to C content to bring up to excessive.
In addition, by implementing quenching and tempering, the intensity of weldless steel tube can be improved.But for low intensive weldless steel tube, if implement quenching and tempering, manufacturing cost raises.
In addition, when the Welded Steel Pipes such as UOE steel pipe, implement the cold working such as tubulation, expander.By cold working, the intensity of Welded Steel Pipe improves, and therefore likely can suppress the generation number of bubble.But as mentioned above, for the line pipe used under the acid environment of harshness, weldless steel tube is suitable.Therefore, be difficult to improve intensity by cold working etc., consider that manufacturing cost is also not preferred.
Therefore, in present embodiment, improve C content, improve Nb content further.Specifically, C content is set to 0.08 ~ 0.24%, Nb content is set to 0.02 ~ 0.12%.Now, even do not implement the weldless steel tube of quenching and tempering (eliminating quenching and tempering), also can improve intensity, the generation of bubble can be suppressed.
More than the F1 value that the numerical value of preferred Nb content (quality %) defines for formula (1).
F1＝0.02+(t-15)×0.001(1)
At this, substitute into the numerical value except unit of the wall thickness (unit mm) of weldless steel tube to t.
The wall thickness of the weldless steel tube of the line pipe purposes used under acid environment is such as 10 ~ 50mm.If wall thickness is thick, the cooling conditions of the weldless steel tube after hot-work also changes.That is, speed of cooling is slack-off, the tendency that the intensity that there is steel reduces.If Nb content is that the F1 value of formula (1) is above, the intensity of steel is more than 350MPa, can suppress the generation of bubble.
The weldless steel tube of the present embodiment completed based on above discovery is as described below.
The weldless steel tube of present embodiment is the line pipe purposes used under acid environment.Above-mentioned weldless steel tube, it possesses following chemical constitution: by mass%, containing C:0.08 ~ 0.24%, Si:0.10 ~ 0.50%, Mn:0.3 ~ 2.5%, below P:0.02%, below S:0.006%, Nb:0.02 ~ 0.12%, Al:0.005 ~ 0.100%, Ca:0.0003 ~ 0.0050%, below N:0.0100%, below O:0.0050%, Ti:0 ~ 0.1%, V:0 ~ 0.03%, Cr:0 ~ 0.6%, Mo:0 ~ 0.3%, Ni:0 ~ 0.4%, Cu:0 ~ 0.3% and B:0 ~ 0.005%, remainder is made up of Fe and impurity, and described weldless steel tube possesses the tissue be made up of ferrite and pearlite, have 350 ~ less than the yield strength of 450MPa.
More than the F1 value that the content (quality %) of preferred Nb defines for formula (1).
F1＝0.02+(t-15)×0.001(1)
At this, substitute into the numerical value except unit of the wall thickness (unit mm) of weldless steel tube to t.
Below the weldless steel tube of present embodiment is described in detail.
[chemical constitution]
The weldless steel tube of present embodiment has following chemical constitution.
C：0.08～0.24％
Carbon (C) improves hardenability, improves the intensity of steel.As the weldless steel tube of present embodiment, do not implement the heat treated situations such as Q-tempering after tubulation under, if C content is too low, the intensity of steel is too low.If C content is too low, and then be difficult to obtain excellent HIC-resistance.If C content is more than 0.08%, the perlite dispersion of high strength is separated out in steel.Therefore ferritic surrender is inhibited.Therefore can obtain excellent HIC-resistance, the generation of bubble is inhibited.On the other hand, the weldless steel tube of present embodiment, as line pipe, carries out boxing at the scene.Therefore, if C content is too high, harden in the heat affected zone (HAZ) of boxing and resistance to SSC reduces.Therefore, C content is 0.08 ~ 0.24%.The preferred lower limit of C content is higher than 0.08%, more preferably 0.10%.The preferred upper limit of C content is less than 0.24%, more preferably 0.15%.
Si：0.10～0.50％
Silicon (Si) is by steel-deoxidizing.If Si content is too low, can not get this effect.On the other hand, if Si too high levels, the toughness of welded heat affecting zone reduces.If Si too high levels, and then promote the ferritic precipitation as softening phase.Therefore, HIC-resistance reduces, and easily produces bubble.Therefore, Si content is 0.10 ~ 0.50%.The preferred lower limit of Si content is higher than 0.10%, is more preferably 0.15%, more preferably 0.20%.The preferred upper limit of Si content is less than 0.50%, is more preferably 0.35%, more preferably 0.30%.
Mn：0.3～2.5％
Manganese (Mn) improves the hardenability of steel, improves the intensity of steel.The toughness of Mn and then raising steel.If Mn content is too low, can not get this effect.On the other hand, if Mn too high levels, the hardening of steel caused due to Mn segregation and the formation of MnS, and easily produce HIC.Therefore Mn content is 0.3 ~ 2.5%.The preferred lower limit of Mn content, higher than 0.3%, is more preferably 0.5%, and more preferably 0.8%.The preferred upper limit of Mn content, less than 2.5%, is more preferably 2.0%, and more preferably 1.8%.
Below P:0.02%
Phosphorus (P) is impurity.P makes the toughness of steel reduce.Therefore, P content is less than 0.02%.Preferred P containing quantity not sufficient 0.02%, more preferably less than 0.01%.P content is preferably low as far as possible.
Below S:0.006%
Sulphur (S) is impurity.S forms MnS.MnS forms the starting point of bubble.Therefore, S content is preferably low.But the reduction of S content needs to spend cost.In the weldless steel tube of present embodiment, in order to suppress manufacturing cost, S content is set to less than 0.006%.In the weldless steel tube of present embodiment, even if S content contains more than 0.005%, if C content and Nb content suitable, excellent HIC-resistance also can be shown, the generation of bubble is inhibited.But S content is preferably low.Preferred S content is less than 0.003%.
Nb：0.02～0.12％
Niobium (Nb) is solid-solution in ferrite and improves the intensity of steel.Nb and then be combined with C and N and form carbonitride, makes steel carry out grain refining by pinning (pinning) sclerosis.By grain refining, the HIC-resistance of steel improves.The toughness of grain refining and then raising steel.After C containing above-mentioned scope and the Mn of above-mentioned scope, the steel tubulation not containing Nb are formed weldless steel tube, do not implement heat treated situation (that is, manufacture the situation of rolling state (asroll) material eliminating quenching and tempering) under, the yield strength of manufactured weldless steel tube is about 250MPa.But if the Nb content containing above-mentioned scope, the yield strength of weldless steel tube is increased to more than 350MPa.Therefore, the generation of bubble is inhibited.If Nb content is too low, can not get above-mentioned effect.On the other hand, if Nb too high levels, form thick Nb carbonitride.Thick Nb carbonitride forms the starting point of bubble, and then HIC-resistance also reduces.Therefore, Nb content is 0.02 ~ 0.12%.
As mentioned above, the wall thickness of the weldless steel tube of the line pipe purposes of acid environment is 10 ~ 50mm.The wall thickness of weldless steel tube is larger, then the speed of cooling of weldless steel tube is slower, and ferrite crystal grain becomes thicker.Therefore, the yield strength of steel reduces.More than the F1 value (%) that therefore preferably the lower limit of Nb content defines for following formula (1).
F1＝0.02+(t-15)×0.001(1)
At this, substitute into the numerical value except unit of the wall thickness (mm) of weldless steel tube to the t in formula (1).
When above-mentioned weldless steel tube meets formula (1), not only mother metal, and also by the welded heat affecting zone that the boxing between weldless steel tube is formed, can guarantee sufficient yield strength, the generation of bubble is inhibited.Speed of cooling after there is heating welded heat affecting zone fast and the hardening region of sclerosis and speed of cooling are slowly and be repeatedly subject to heat affecting and softening softened region.When meeting above-mentioned formula (1), in softened region, fully yield strength guaranteed.
The preferred lower limit of Nb content is higher than 0.02%, is more preferably 0.03%, more preferably 0.04%.The preferred upper limit of Nb content is less than 0.12%, is more preferably 0.10%, more preferably 0.08%.
Al：0.005～0.100％
Aluminium (Al) is by steel-deoxidizing.If Al content is too low, can not get this effect.On the other hand, if Al too high levels, form the alumina inclusion composition granule of thick group (cluster) shape during boxing, the toughness in welded heat affecting zone (HAZ) reduces.Therefore, Al content is 0.005 ~ 0.100%.The preferred lower limit of Al content is higher than 0.005%, is more preferably 0.010%, more preferably 0.020%.The preferred upper limit of Al content is less than 0.100%, is more preferably 0.060%, more preferably 0.040%.In this specification sheets, Al content refers to the content of sour solvable Al (sol.Al).
Ca：0.0003～0.0050％
Calcium (Ca) suppresses the blocking of tundish nozzle when casting.Ca and then suppression form the generation of the MnS of the starting point of HIC, bubble and fine internal fissure.Therefore, Ca suppresses the generation of bubble and fine internal fissure.If Ca content is too low, this effect is insufficient.On the other hand, if Ca too high levels, inclusion forms group, and the toughness of steel and HIC-resistance reduce.Therefore, Ca content is 0.0003 ~ 0.0050%.The preferred lower limit of Ca content is higher than 0.0003%, is more preferably 0.0010%, more preferably 0.0015%.The preferred upper limit of Ca content is less than 0.0050%, is more preferably 0.0040%, more preferably 0.0030%.
Below N:0.0100%
Nitrogen (N) is impurity.N forms thick nitride and the toughness of steel and resistance to SSC is reduced.Therefore, N content is preferably low.Therefore, N content is less than 0.0100%.Preferred N content is less than 0.0080%, more preferably less than 0.0060%.
Below O:0.0050%
Oxygen (O) is impurity.O forms the group of thick oxide compound or oxide compound and the toughness of steel and HIC-resistance is reduced.Therefore, O content is preferably low as far as possible.Therefore, O content is less than 0.0050%.Preferred O content is less than 0.0040%, more preferably less than 0.0030%.
The remainder of the chemical constitution of the weldless steel tube of present embodiment is made up of Fe and impurity.Impurity alleged by this refers to the element be mixed into by the environment etc. of the ore of the prepared using as steel, waste material or manufacturing processed.
[about selection element]
The weldless steel tube of present embodiment can also containing be selected from the group that is made up of Ti, V, Cr, Mo, Ni, Cu and B one or more.These elements all improve the intensity of steel.
Ti：0～0.1％
Titanium (Ti) is for selecting element.Ti and Nb is similarly combined with C and N and forms carbonitride, is hardened by pinning, and steel is carried out grain refining.On the other hand, if Ti too high levels, its effect is saturated.Therefore, Ti content is 0 ~ 0.1%.The preferred lower limit of Ti content is 0.002%, more preferably 0.005%.The preferred upper limit of Ti content is less than 0.1%, more preferably 0.05%.
V：0～0.03％
Vanadium (V) is for selecting element.V-arrangement becomes carbide, and steel is strengthened.On the other hand, if V too high levels, form thick carbide and easily produce SSC.Therefore, V content is 0 ~ 0.03%.The preferred lower limit of V content is 0.01%, more preferably 0.015%.The preferred upper limit of V content is less than 0.03%, more preferably 0.025%.
Cr：0～0.6％
Mo：0～0.3％
Ni：0～0.4％
Cu：0～0.3％
Chromium (Cr), molybdenum (Mo), nickel (Ni) and copper (Cu) are all select element.These elements all improve the hardenability of steel and steel are strengthened, and in Medium And Low Strength Steels, improve HIC-resistance.On the other hand, if the too high levels of these elements, local produces sclerotic tissue or becomes the reason of steel surface non-uniform corrosion.Therefore, Cr content is 0 ~ 0.6%, Mo content be 0 ~ 0.3%, Ni content be 0 ~ 0.4%, Cu content is 0 ~ 0.3%.The preferred lower limit of Cr content is 0.01%, more preferably 0.05%.The preferred lower limit of Mo content is 0.01%, more preferably 0.05%.The preferred lower limit of Ni content is 0.01%, more preferably 0.05%.The preferred lower limit of Cu content is 0.01%, more preferably 0.05%.The preferred upper limit of Cr content is less than 0.6%, more preferably 0.5%.The preferred upper limit of Mo content is less than 0.3%, more preferably 0.25%.The preferred upper limit of Ni content is less than 0.4%, is more preferably 0.3%, more preferably 0.25%.The preferred upper limit of Cu content is less than 0.3%, more preferably 0.25%.
The total content of preferred Cr, Mo, Ni, Cu meets following formula (2).
(Cr+Mo)/5+(Cu+Ni)/15<0.10(2)
The content (quality %) of the element corresponding to substituting into each symbol of element in formula (2).
If Cr, Mo, Ni and Cu meet formula (2), even the weldless steel tube of heavy wall, yield strength are also less than 450MPa.
B：0～0.005％
Boron (B) is for selecting element.B, in low intensive weldless steel tube, improves the hardenability of steel, in Medium And Low Strength Steels, improves HIC-resistance.On the other hand, if B too high levels, the resistance to SSC of steel reduces.Therefore, B content is 0 ~ 0.005%.The preferred lower limit of B content is more than 0.0001%, more preferably 0.0003%.The preferred upper limit of B content is less than 0.005%, more preferably 0.003%.
[tissue and intensity]
The weldless steel tube of present embodiment does not implement quenching and tempering after tubulation.That is, the weldless steel tube of present embodiment is the so-called rolling state material eliminating quenching and tempering.As described later, the weldless steel tube naturally cooling after tubulation or cool with the speed of cooling less than 2 DEG C/s.Therefore, the tissue of the weldless steel tube of present embodiment is made up of ferrite and pearlite.The major part of tissue is ferrite, remainder is perlite.Tissue alleged by this refers to the parent phase tissue not containing inclusion and precipitate.
Even if cool with above-mentioned slow speed of cooling, the weldless steel tube of present embodiment also has the yield strength of more than 350MPa.In this specification sheets, yield strength refers to 0.2% offset yield strength.The preferred yield strength of weldless steel tube is more than 400MPa.It should be noted that, in the weldless steel tube of present embodiment, yield strength is less than 450MPa.
[manufacture method]
One example of the manufacture method of the line-pipes weldless steel tube used under the acid environment of present embodiment is described.
By the steel melting of above-mentioned chemical constitution, with known method refining.Then, by Continuous casting process, molten steel is formed continuous cast materials.Continuous cast materials is such as slab, bloom, small billet.In addition, also by ingot casting method, molten steel can be formed steel ingot.
Hot-work is carried out to the slab in continuous cast materials, bloom and steel ingot, manufactures small billet.Such as by slab, bloom, steel ingot cogging, manufacture small billet.
Then, manufactured small billet is carried out hot tubulation, manufacture weldless steel tube.Specifically, with process furnace, small billet is heated.If for the small billet through heating, under the state of residual thick Nb inclusion, implement hot tubulation, then, during cooling after hot tubulation, fully can not obtain the strengthening utilizing Nb to realize.Therefore, in present embodiment, compared with during manufacture with common weldless steel tube, be heated to high temperature further.Specifically, during above-mentioned heating, small billet is heated to more than 1250 DEG C.
Hot-work is implemented for the small billet extracted out by process furnace, manufactures weldless steel tube.Specifically, implement the pierced billet based on Mannesmann's method, manufacture pipe.For manufactured pipe, and then implement drawing/rolling and fixed diameter rolling by mandrel mill, speed reduction unit, sizing mill etc., manufacture weldless steel tube.
Weldless steel tube through tubulation is cooled.Now, preferably, the speed of cooling of the high temperature range of more than 500 DEG C of Nb Carbonitride Precipitation is fast.Therefore, till the temperature of weldless steel tube is 500 DEG C, with the speed of cooling of 0.5 ~ 5 DEG C/s cooling weldless steel tube, then with the speed of cooling cooling less than 2 DEG C.Also naturally cooling is comprised less than the speed of cooling of 2 DEG C/s.
Above-mentioned speed of cooling such as can be adjusted by the interval of adjacent weldless steel tube during adjustment naturally cooling.Such as, till weldless steel tube is 500 DEG C, the interval of adjacent weldless steel tube is set to distance D1, when being below 500 DEG C, is above-mentionedly intervally adjusted to the distance D2 shorter than distance D1.Two stage speed of cooling slowly can be realized thus.
In above-mentioned manufacture method, for the weldless steel tube after hot-work, do not implement quenching and temper.
[bubble number]
For the weldless steel tube by above manufacture method manufacture, the generation of bubble can be suppressed.When particularly the F1 value that defines for formula (1) of Nb content (%) is above, the bubble number in surface is less than 10/20cm 2.At this, bubble number can be obtained by bubble number determination test shown below.
[bubble number determination test]
Based on the NACETM0284-2011 specified by international corrosion engineering Shi Xiehui (NACE, NationalAssociationofCorrosionEngineers) International of the U.S., implement the HIC test using moistening hydrogen-sulfide environmental (acid environment).Specifically, the corrosion test sheet of thickness of slab × 20mm width × 100mm length (length of the axis of weldless steel tube) is gathered by weldless steel tube.Above-mentioned corrosion test sheet has an effects on surface of outside surface and the internal surface being equivalent to weldless steel tube.
According to NACETM0284, prepare in normal atmosphere at 5%NaCl+0.5%CH 3in the COOH aqueous solution saturated 100% H 2the test bath of 25 DEG C of S gas.Immersion corrosion experiment sheet is bathed 96 hours in test.Flood after 96 hours, the surface (being equivalent to the two sides of the internal surface of weldless steel tube and the 20mm width × 100mm length of outside surface) of visual inspection corrosion test sheet.Then the sum of the bubble resulting from above-mentioned surface is counted, obtain bubble number (individual/20cm 2).
As mentioned above, in the weldless steel tube of present embodiment, by C and Nb, yield strength is brought up to more than 350MPa, the generation of bubble can be suppressed thus.Therefore, HIC-resistance is excellent, and then not easily produces SOHIC during load tensile stress.
Embodiment
Manufacture the steel ingot of the steel A1 ~ A15 shown in table 1, B1 ~ B6.
"-" expression in table 1 is essentially " 0 " % (impurity level).F2 in table 1 definition as described below.
F2＝(Cr+Mo)/5+(Cu+Ni)/15
In a word, F2 is the left side of formula (2).
With reference to table 1, the chemical constitution of steel A1 ~ steel A15 is in the scope of the chemical constitution of the weldless steel tube of present embodiment.On the other hand, the Nb of steel B1 and steel B3 not containing Nb, steel B2 is containing the lower limit of the Nb content of quantity not sufficient present embodiment.The lower limit of the C content of the weldless steel tube of the not enough present embodiment of C content of steel B4 and steel B5.The F2 of steel grade class B6 does not meet formula (2).
By the steel ingot forge hot of each steel, for the multiple small billet of each steel making.After heating under the Heating temperature of small billet shown in table 2, use tapping machine (piercer) by small billet pierced billet, manufacture weldless steel tube.Now, for each steel, manufacture three kinds of weldless steel tubes of wall thickness=12.7mm, 25.4mm and 38.1mm.For the weldless steel tube after manufacture, till the temperature of weldless steel tube is 500 DEG C, with the first speed of cooling cooling shown in table 2, after this cool with the second speed of cooling.
[microstructure observation's test]
For the weldless steel tube of three kinds of wall thickness manufactured by each steel, implement microstructure observation's test.In the transverse section (face perpendicular to the axis of weldless steel tube) of each weldless steel tube, wall thickness middle body nital etc. is etched.Observe any visual field (visual field area 40000 μm through overetched wall thickness middle body 2).Observe the opticmicroscope of use 500 times.
The result of microstructure observation's test, in any weldless steel tube, has the tissue be made up of ferrite and pearlite.
[yield strength test]
By three kinds of weldless steel tubes of each steel, gather the pole tension test sheet of parallel portion with external diameter 6mm, length 40mm respectively.Parallel portion is parallel in the axis of weldless steel tube.Use the pole tension test sheet gathered, carry out tension test under normal temperature (25 DEG C), obtain yield strength YS (0.2% offset yield strength) (MPa).
[bubble number determination test]
For three kinds of weldless steel tubes of each steel, implement above-mentioned bubble number determination test respectively, obtain bubble number.
[test-results]
Table 2 illustrates test-results.And then Fig. 2 is the photograph image on two surfaces (being equivalent to outside surface and the internal surface of weldless steel tube) of corrosion test sheet after the bubble number determination test of steel A4 (wall thickness 20mm), Fig. 3 is the surperficial photograph images of two of corrosion test sheet after the bubble number determination test of steel B3 (wall thickness 20mm).In Fig. 2 and Fig. 3, the surface of epimere is equivalent to the outside surface of weldless steel tube, and the surface of hypomere is equivalent to the internal surface of weldless steel tube.
With reference to table 2, the chemical constitution of steel A1 ~ A11, A14 and A15 is suitable.Therefore, for the weldless steel tube that wall thickness is the 12.7mm of below 15mm, yield strength YS is 350 ~ less than 450MPa.Therefore, as shown in Figure 2, the generation of the bubble in surface is inhibited, bubble number is less than 10/20cm 2.
And then the Nb content of steel A1 ~ A9 and A11, A14 and A15, more than the F1 value defined for formula (1) in the weldless steel tube of wall thickness 25.4mm.Therefore, even wall thickness is more than the weldless steel tube of 15mm, also can obtain 350 ~ less than the yield strength of 450MPa, bubble number is less than 10/20cm 2.
And then the Nb content of steel A2 ~ A9, A14 and A15, for more than F1 value in the weldless steel tube of wall thickness 38.1mm.Therefore, even wall thickness is more than the weldless steel tube of 35mm, also can obtain 350 ~ less than the yield strength of 450MPa, bubble number is less than 10/20cm 2.
On the other hand, the chemical constitution of steel A12 and A13 is suitable, but for steel A12, Heating temperature is too low, and for steel A13, the first speed of cooling is excessively slow.Therefore, yield strength YS is less than 350MPa, and in the weldless steel tube of any one wall thickness, bubble number is all 10/20cm 2above.
On the other hand, the Nb content of steel B1 ~ B3 is too low.Therefore, even wall thickness is less than the weldless steel tube of 20mm, yield strength is also less than 350MPa.Its result, as shown in Figure 3, produce numerous air-bubble on surface, bubble number is 10/20cm 2above.
In addition, the C content of steel B4 and B5 is too low.Therefore, even wall thickness is less than the weldless steel tube of 20mm, yield strength is also less than 350MPa, and bubble number is 10/20cm 2above.
The F2 value of steel B6 does not meet formula (2).Therefore, the yield strength of steel B6 is more than 450MPa.
Above embodiments of the present invention are illustrated, but above-mentioned embodiment is only for implementing illustration of the present invention.Thus, the present invention not limit by above-mentioned embodiment, not departing from the scope of its aim, above-mentioned embodiment suitably can be out of shape and implement.

Claims (2)

1. the line-pipes weldless steel tube used under acid environment, it possesses following chemical constitution: by mass%, contains
C：0.08～0.24％、
Si：0.10～0.50％、
Mn：0.3～2.5％、
Below P:0.02%,
Below S:0.006%,
Nb：0.02～0.12％、
Al：0.005～0.100％、
Ca：0.0003～0.0050％、
Below N:0.0100%,
Below O:0.0050%,
Ti：0～0.1％、
V：0～0.03％、
Cr：0～0.6％、
Mo：0～0.3％、
Ni：0～0.4％、
Cu:0 ~ 0.3% and
B：0～0.005％，
Remainder is made up of Fe and impurity,
And described weldless steel tube possesses the tissue be made up of ferrite and pearlite,
Have 350 ~ less than the yield strength of 450MPa.
2. weldless steel tube according to claim 1, wherein, more than the F1 value that the content of described Nb defines for formula (1), wherein the unit of content is quality %,
F1＝0.02+(t-15)×0.001(1)
At this, substitute into the numerical value except unit of the wall thickness of weldless steel tube to t, wherein the unit of wall thickness is mm.
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