CN1688726A - High strength seamless steel pipe excellent in hydrogen-induced cracking resistance and its production method - Google Patents
High strength seamless steel pipe excellent in hydrogen-induced cracking resistance and its production method Download PDFInfo
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- CN1688726A CN1688726A CN 03823580 CN03823580A CN1688726A CN 1688726 A CN1688726 A CN 1688726A CN 03823580 CN03823580 CN 03823580 CN 03823580 A CN03823580 A CN 03823580A CN 1688726 A CN1688726 A CN 1688726A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 197
- 239000010959 steel Substances 0.000 title claims abstract description 197
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 19
- 239000001257 hydrogen Substances 0.000 title claims abstract description 19
- 238000005336 cracking Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 238000010791 quenching Methods 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 18
- 238000005496 tempering Methods 0.000 claims abstract description 17
- 230000000171 quenching effect Effects 0.000 claims abstract description 16
- 229910001563 bainite Inorganic materials 0.000 claims abstract description 15
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 16
- 230000001376 precipitating effect Effects 0.000 claims description 13
- 238000005098 hot rolling Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 abstract description 15
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 15
- 239000011575 calcium Substances 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 10
- 239000011572 manganese Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 235000009508 confectionery Nutrition 0.000 description 7
- 239000010779 crude oil Substances 0.000 description 7
- 239000003345 natural gas Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000010955 niobium Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000003129 oil well Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000006355 external stress Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000010079 rubber tapping Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- -1 MnS etc. Chemical compound 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a high strength seamless steel pipe excellent in hydrogen-induced cracking resistance, characterized by consisting of, by mass %, C: 0.03 - 0.11 %, Si: 0.05 - 0.5 %, Mn: 0.8 - 1.6 %, P: 0.025 % or less, S: 0.003 % or less, Ti: 0.002 - 0.017 %, Al: 0.001 - 0.10 %, Cr: 0.05 - 0.5 %, Mo: 0.02 - 0.3 %, V: 0.02 - 0.20 %, Ca: 0.0005 - 0.005 %, N: 0.008 % or less and O (Oxygen): 0.004 % or less, and the balance Fe and impurities, and also characterized in that the microstructure of the steel is bainite and/or martensite, ferrite is precipitated at grain boundaries and yield stress is 483 MPa or more. Further, to ensure high strength of the steel, the seamless steel pipe preferably contains, by mass %, at least one of Cu: 0.05 - 0.5 % and Ni: 0.05 - 0.5 %. To produce the above-mentioned steel pipe, it is desirable to limit a starting temperature of quenching after rolling, a cooling rate and a tempering temperature. By this configuration a seamless steel pipe having an yield stress of 483 MPa or more and excellent HIC resistance, which is suitable for a pipeline, can be provided.
Description
Technical field
The present invention relates to have excellent in hydrogen-induced cracking resistance energy (hydrogen-induced crackingresistance, be called " anti-HIC " below) weldless steel tube, it is as having the 5L-X70 grade or than American Petroleum Institute (API) the standard pipeline steel pipe of high strength grade more.
Background technology
In recent years, being used for the become transportation of harsh day by day and crude oil and Sweet natural gas of the oil well of crude oil and the condition in the well of gas well (being commonly referred to as " oil well etc. " hereinafter) of Sweet natural gas of being used for carries out under severe environment.Along with the increase of water depth, condition is tending towards containing CO in the well of oil well etc.
2, H
2S, Cl
-And other material in the environment, and often comprise H in crude oil and the Sweet natural gas
2S.
When oil well etc. is in the seabed,, require high strength and thick wall thickness can support submarine hydraulic pressure at the offshore pipeline steel pipe along with the increase of water depth.Because the offshore pipeline steel pipe is in so dark sea, therefore use gapless stainless steel tube usually.
Comprise a large amount of H being used for transportation
2In the crude oil of S or the pipeline steel pipe of Sweet natural gas, not only because H
2S is to the corrosion of steel material surface, thereby and because the hydrogen adsorption that corrosion produces causes fracture phenomenon such as the hydrogen induced cracking (HIC) or the hydrogen blistering etc. (common name work " HIC " hereinafter) of steel in the steel.This HIC is different with sulfide-stress cracking, and the latter is present in the high-strength steel usually, and the former does not depend on external stress, therefore thinks HIC to occur under the situation that does not have external stress.
When this HIC appears in the transport pipeline, will cause the break accident of pipeline.As a result, the leakage owing to crude oil or Sweet natural gas causes occurring large-scale environmental disruption.Therefore, at the transport pipeline that is used for crude oil or Sweet natural gas, important thing is the appearance that prevents HIC.
HIC above-mentioned is the steel fracture phenomenon, i.e. inclusion such as MnS, the Al that exists in steel during steel rolling
2O
3, CaO, CaS be elongated or be crushed to the cluster shape in rolling direction, the hydrogen that absorption enters interface between these inclusiones and the matrix steel (matrix steel) is gathered and is gasified, the gaseous tension of accumulating hydrogen has produced cracking, and these crackings spread in steel.
In order to prevent to show the HIC of such behavior in steel, the someone has proposed the various steel that are applied in the pipeline steel pipe.For example, such steel that is used for pipeline steel pipe has been proposed among the Japanese Patent Application Publication S50-97515, wherein the Cu that the steel of X42-X80 grade strength adds 0.2-0.8% in having the API standard prevents thus that to form erosion-resisting film hydrogen is inhaled in the matrix steel.
In addition, a kind of steel that is used for pipeline steel pipe has been proposed among the Japanese Patent Application Publication S53-106318, wherein will join in the steel above the Ca (this is relatively large) of 0.005-0.020 or littler %, and make inclusion (MnS) spheroidization in the steel by the shape control (shape control) that Ca handles, reduced cracking sensitivity thus.Even present anti-HIC steel also is to prepare on the basis of these proposed techniques.
In addition, because anti-HIC steel is mainly used in the transport pipeline of crude oil and Sweet natural gas, so weldability is very important.Therefore, soft steel is applied in the anti-HIC steel, but is difficult to obtain high-strength steel owing to the carbon content of steel is low.On the other hand, as mentioned above, the user needs high-strength material.Therefore,, often carry out following step in order to satisfy the demands: by hot rolling with steel pipe finish rolling after, with steel pipe heating and quench, carry out tempering subsequently.
This quenching that wroughtsteel pipe is carried out and temper are effective for ferrite and the pearlitic banded microstructure of avoiding wherein being easy to occurring HIC.
As mentioned above, be used for the steel of pipeline steel pipe, weldability is very important, and requires high strength.Therefore, after hot rolling, wroughtsteel pipe quenches and tempering usually.In addition, in seamless steel tube production, consider, the finish rolling steel pipe be not cooled to Ar from the viewpoint of suppression equipment Cost Growth and production efficiency
3Under the situation of point, consider by making the pipeline rolling line directly be connected (hereinafter only being called " press quenching/tempering (QT) " sometimes) after soaking, to adopt application quenching and tempered to handle with heat-treatment lines.
Therefore, in order to improve the anti-HIC of the high-strength steel material that is used for pipeline steel pipe, handle the steel that carries out shape control by Ca at the wherein inclusion (MnS) that had before proposed by use and carry out wroughtsteel pipe not being cooled to Ar after the hot rolling
3Under the situation of point, the quenching and tempering of the weldless steel tube of high-strength material after by even heat produced.Yet, observe the HIC that the transgranular fracture form occurred showing as.Therefore, even the anti-HIC steel of suggestion is applied in the high-strength steel among the above-mentioned Japanese Patent Application Publication S53-106318 etc., anti-HIC also differs and improves surely.
Summary of the invention
The present invention obtains after the production of the weldless steel tube with high strength and anti-HIC is explored, so the object of the invention provides a kind of high-strength seamless steel pipe and production method thereof that can show excellent anti HIC.
For addressing the above problem, the inventor has put the knowledge of the relevant HIC behavior that occurs in order in pipeline steel pipe.
As described above, HIC is broken by the steel that hydrogen induced cracking or hydrogen blistering cause, it is to be produced by the following fact: the hydrogen absorption that is produced by corrosion enters in the steel, and accumulation and gasification on inclusion in steel and the interface between the matrix steel, and thereby this gaseous tension is increased to above the yield strength of steel and produces the crack, and the crack is spread in steel again.
Therefore, at traditional technical elements, for example, carry out inclusion shape control etc. so that absorb hydrogen and almost can not gasify.Yet for 5L-X70 with API or more high-grade high-strength steel, the starting point of all HIC is not on inclusion, but the HIC crackle shows breaking of similar sulfide-stress cracking, and can show the form of transgranular fracture.
Therefore, further study the anti-HIC of steel and the relation of its quenched microstructure aspect.The result, even recent findings aspect bainite and/or martensitic quenched microstructure, by with the ferrite precipitating to crystal boundary preventing crystal boundary fragility, even and minute crack appears in steel, fissured spreading also can be suppressed, and obtains to have the weldless steel tube of excellent anti HIC thus.
The present invention is based on above-described knowledge and finish, main points of the present invention are following production methods (3) of following high-strength seamless steel pipe (1) and (2) and described high-strength seamless steel pipe.
(1) a kind of high-strength seamless steel pipe that excellent anti HIC is arranged, it is characterized in that by following the composition (in quality %): C:0.03-0.11%, Si:0.05-0.5%, Mn:0.8-1.6%, P:0.025% or still less, S:0.003% or still less, Ti:0.002-0.017%, Al:0.001-0.1%, Cr:0.05-0.5%, Mo:0.02-0.3%, V:0.02-0.20%, Ca:0.0005-0.005%, N:0.008% or still less and O (oxygen): 0.004% or still less, surplus is Fe and impurity, its feature is that also the microtexture of steel is bainite and/or martensite, the ferrite precipitating is to crystal boundary, and yielding stress is 483MPa or higher.
(2) a kind of high-strength seamless steel pipe except that the above-mentioned weldless steel tube of mentioning (1), it also preferably comprises (in the quality %) Cu of at least a 0.05-0.5% and the Ni of 0.05-0.5%.
(3) a kind of production method of high-strength seamless steel pipe of anti-HIC excellence, it is characterized in that having described in above-mentioned (1) and (2) steel billet formed becomes after the weldless steel tube by hot rolling, and the even immediately heat of described weldless steel tube is then at (Ar
3Point+50 ℃) to 1100 ℃ quenching temperatures down and with 5 ℃/second or higher rate of cooling cooling, described then weldless steel tube at 550 ℃ to Ac
1The point tempering, produce so a kind of weldless steel tube thus: the microtexture of steel is bainite and/or martensite, the ferrite precipitating is to crystal boundary, and yielding stress is 483MPa or higher.
Description of drawings
Figure 1 shows that the microtexture photo of the weldless steel tube that anti-HIC is relatively poor; With
Figure 2 shows that the microtexture photo of the weldless steel tube of anti-HIC excellence.
Embodiment
To explain below as recited above those of the present invention and limit the reason of chemical constitution, the microtexture and the production method of steel pipe.At first, the reason that limits weldless steel tube chemical constitution of the present invention is described.In the following description, chemical constitution is represented with quality %.
1. the chemical constitution of steel
C：0.03-0.11％
C (carbon) is the bioelement that improves the hardenability of steel and improve intensity.When C content less than 0.03% the time, hardenability reduces, and high strength is difficult to guarantee.On the other hand, when C content surpassed 0.11%, under the situation of using QT, steel trended towards having microtexture such as bainite and/or the martensite etc. that quench fully, thereby the not only anti-HIC reduction of steel, and weldability also reduces.
Si：0.05-0.5％
Si (silicon) joins in the steel for the deoxidation purpose of steel, and it helps to improve intensity and improves the softening resistance of steel during tempering.In order to obtain these effects, need adding 0.05% or more Si.Yet, because add the snappiness that excessive Si can reduce steel, so the content of Si is set at 0.5% or still less.
Mn：0.8-1.6％
Mn (manganese) is the effective element that a kind of hardenability that is used to improve steel improves its intensity and improves the hot workability of steel.Especially, in order to improve the hot workability of steel, must adding 0.8% or more Mn.Yet, because add snappiness and the weldability that excessive Mn can reduce steel, so the content of Mn is set at 1.6% or still less.
P:0.025% or still less
P (phosphorus) exists as impurity in steel.Because the snappiness of the P segregation on crystal boundary reducing steel, so P content is set at 0.025% or still less.P content preferred 0.015% or still less, more preferably 0.009% or still less.
S:0.003% or still less
S (sulphur) exists as impurity in steel.Because S produces sulfide such as MnS etc., and reduces anti-HIC, so S content is set at 0.003% or still less.S content preferred 0.002% or still less, more preferably 0.001% or still less.
Ti：0.002-0.017％
Ti (titanium) prevents the fissured element of steel billet effectively.In order to show this effect, the content of Ti need be 0.002% or more.On the other hand, because add the snappiness that excessive Ti can reduce steel, so Ti content is set at 0.017% or still less, and preferred 0.010% or still less.
Al：0.001-0.10％
Al (aluminium) is the essential element that is used for the deoxidation of steel.When Al content too hour, it is insufficient that deoxidation becomes, and produce surface imperfection on steel billet, deterioration the performance of steel.Therefore, Al content is set at 0.001% or more.On the other hand, can produce the crack because add excessive Al in steel billet, this will cause rigidity energy variation.Therefore Al content is set at 0.10% or still less, and preferred 0.040% or still less.
Cr：0.05-0.5％
Cr (chromium) is the element that is used to improve hardness of steel.By add 0.05% or more Cr can obtain unusual effect.Yet even because excessive adding Cr, this effect also can only be saturated on certain level, so Cr content is set at 0.5% or still less.
Mo：0.02-0.3％
Mo (molybdenum) is the element that is used to improve hardness of steel.Interpolation 0.02% or more Mo can obtain unusual effect.Yet even because excessive adding Mo, this effect also can only be saturated on certain level, so Mo content is set at 0.3% or still less.
V：0.02-0.20％
V (vanadium) is the element that is used to improve hardness of steel.By add 0.02% or more V can obtain unusual effect.Yet even because excessive adding V, this effect also can only be saturated on certain level, so V content is set at 0.20% or still less, preferred 0.09% or still less.
Ca：0.0005-0.005％
Ca (calcium) is used for the control of inclusion shape.Improve anti-HIC by sphering MnS inclusion, Ca content needs 0.0005% or more.On the other hand, when Ca content surpassed 0.005%, this effect can not have further effect with saturated.In addition, the Ca inclusion trends towards agglomerating so that anti-HIC decline.Therefore, the upper limit of Ca content is set at 0.005%.
N:0.008% or still less
N (nitrogen) exists as impurity in steel.When N content increases, on steel billet, produce crack so that rigidity energy variation.Therefore N content is set at 0.008% or still less.Preferred N content is 0.006% or still less.
O (oxygen): 0.004% or still less
O content mean can be in steel dissolved oxygen and in oxide inclusion the total content of oxygen.This oxygen level is identical with oxygen level in the oxide inclusion in the steel of fully deoxidation basically.Therefore, when O content increases, the oxide inclusion in steel will increase, thereby reduce anti-HIC.Therefore, O content is the smaller the better, so O content is set at 0.004% or still less.
Cu (copper): 0.05-0.5%, Ni (nickel): 0.05-0.5%
These elements all are the elements that is used to improve hardness of steel.Therefore, in the time that hardness of steel should be guaranteed, can comprise in these two kinds of elements one or both.Cu, Ni content all are 0.05% or more for a long time, it is obvious that this effect becomes.Yet even any in excessive adding two elements, this effect also all can be saturated, so the content of every kind of element all is set at 0.5% or still less.
Nb:Nb (niobium) content can be not influential to the anti-HIC and the intensity of steel.Therefore the Nb element can be considered as impurity element, and its content is also unqualified in the present invention.Yet when Nb content surpasses 0.1%, the snappiness deterioration of some undesired effects such as steel will become clearly.Therefore Nb content range preferred 0.1% or still less.
2. the production method of steel pipe microstructure and it
In weldless steel tube of the present invention, by using the steel of the relatively low C shown in the chemical constitution as mentioned above, steel pipe microstructure must be quenched microstructure such as bainite and/or martensite, to guarantee 5L-X70 or more high-grade intensity.In order to obtain this microtexture, the online QT of advantageous applications.
Yet, because the microtexture of having only bainite and/or martensite to quench fully trends towards producing HIC (this HIC is presented as a kind of transgranular fracture form such as sulfide-stress cracking), so the precipitating ferrite is very important on crystal boundary.
In the present invention, the ferrite precipitating has the effect that prevents that HIC from producing on bainite and/or martensitic crystal boundary, and this HIC is presented as a kind of form such as sulphide stress corrosion crack of transgranular fracture, has guaranteed 5L-X70 or more high-grade intensity simultaneously.
Figure 1 shows that the microtexture photo of the weldless steel tube that anti-HIC is relatively poor.The microtexture of Fig. 1 is by the etched structure of Nai Taer nital, and it embodies bainite and/or the complete quenched microstructure of martensite, can clearly discern austenite grain boundary formerly therein.Under the situation of this microtexture, trend towards producing the HIC that shows as transgranular fracture form such as sulfide-stress cracking form.
On the contrary, Figure 2 shows that and relate to the microtexture photo with weldless steel tube of excellent anti HIC of the present invention.Same as in figure 1, Figure 2 shows that by the etched microtexture of Nai Taer nital.Because ferritic phase produces on crystal boundary, so original austenite grain boundary is unsharp in microtexture.Under the situation of this microtexture, just can not show as the HIC of transgranular fracture form.
In the present invention, use the steel billet comprise the chemical constitution that the present invention limits the time, can obtain weldless steel tube in excellence aspect the promptly anti-HIC of target capabilities by limiting above-mentioned microtexture as material.A kind of preferred preparation method that is used to obtain weldless steel tube is shown below, and this method side by side satisfies microtexture and high strength.
That is to say, make steel billet heating and its finish rolling is become after the steel pipe shape that institute's steel pipe that obtains is it is being cooled to Ar by hot-work
3Use the even immediately (Ar that is heat-treated to of soaking pit under the situation of point
3Point+50 ℃) temperature or higher is quenched then.
When the starting temperature of quenching less than (Ar
3Point+50 ℃) time, intensity changes.On the other hand, when the starting temperature of quenching increased, the snappiness of steel pipe significantly reduced.Therefore, the starting temperature of quenching must be 1100 ℃ or lower, and therefore, the starting temperature of quenching is set at (Ar
3Point+50 ℃) to 1100 ℃.
The quenching of finish rolling steel pipe is undertaken by it being cooled to for example room temperature, keeps 5 ℃/second rate of cooling simultaneously.Rate of cooling during quenching can not guarantee need to obtain the needed microtexture that comprises martensite and bainite of intensity during less than 5 ℃/second.Therefore, should keep 5 ℃/second or higher rate of cooling.
For the intensity of the welding region that prevents to be influenced by heat reduces, need 550 ℃ or higher tempering temperature.Yet, when tempering temperature surpasses Ac
1During point, the intensity of steel pipe reduces.Therefore, tempering must be at 550 ℃ to Ac
1Finish under the temperature condition of point.
The present invention is for up to the production stage that is become steel pipe by the finish rolling of starting material steel billet without limits.As alternatives, (for example) by adopt as Mannesmann's mandrel mill (Mannesmann-mandrel mill) processing by steel billet by rolling acquisition in blooming mill after the steel billet of continuous caster casting or the heating foundry goods and the hollow bloom by tapping machine such as skew rolling mill acquisition.Plug be inserted into be rolled in the pipe after, use sizing mill or sinking mill to carry out finish rolling.
Note, having the chemical constitution of qualification in (1) of the present invention and (2) and the weldless steel tube of microtexture and also can obtain anti-HIC of the present invention even in the production method the mode of production of in (3) of the present invention, describing.
(embodiment 1)
Steel with some kinds of chemical constitution shown in the table 1 melts by converter.Steel billet by continuous casting production is heated to 1100 ℃ or higher, then by using the tilting roller tapping machine to obtain hollow bloom.Finish rolling becomes steel pipe to these hollow blooms with sizing mill by the core rod type milling train.Then, be not cooled to Ar at steel pipe
3Under point or the lower situation, these steel pipes are 950 ℃ of even down warm, and quench and temper, thereby produce weldless steel tube.Steel pipe sizes and heat-treat condition are table 2 illustrate.In this case, rate of cooling is set at 30 ℃/second.
The Elongation test sample of preparation JIS 12 is used for Elongation test from the steel pipe that is obtained, and measures tensile strength (TS) and yield strength (YS).Notice that Elongation test carries out according to JIS Z 2241.
In addition, getting thickness is that 12～20mm, the wide 20mm of being, length are used for anti-HIC test for the sample of 100mm.Sample has a H saturated
2The 0.5%CH of S
3(temperature is 25 ℃, pH=2.7-4.0, usually said NACE environment) soaked about 96 hours in the aqueous solution of COOH-5%NaCl, and measured crack area ratio (CAR (%)).These results are table 2 illustrate.
In addition, after anti-HIC property testing, cut away the cross section of HIC specimen and pass through their microtexture of observation by light microscope.The observed result that obtains is table 2 illustrate.
As can be seen from Table 2, satisfy the intensity of 5L-X70 grade according to all numbering steel capital of 1～14 of the embodiment of the invention, and have the excellent state of CAR=0%.
On the other hand, numbering 15 steel has C and the O content that exceeds institute of the present invention limited range in comparing embodiment, and ferrite do not have precipitating to the interface, obtains the deteriorated result of CAR=12.6% thus.And number that C content has also exceeded prescribed value of the present invention in 16 the steel, and ferrite do not exist on crystal boundary yet, thereby obtain the deteriorated result of CAR=7.9%.
In addition, the steel of numbering 17 has the O content that exceeds prescribed value of the present invention in comparing embodiment, and causes obtaining the deteriorated result of CAR=6.2% owing to inclusion.The steel of numbering 18 has the Ca content that exceeds prescribed value scope of the present invention, and causes the deteriorated result of CAR=3.6% owing to inclusion.
Table 1
| Steel numbering system | Chemical constitution (quality %) surplus: Fe and impurity | ||||||||||||||
| ??C | ??Si | ??Mn | ??P | ??S | ??Ti | ??Al | ??Ca | ??N | ??O | ??Cu | ??Cr | ??Ni | ??Mo | ??V | |
| ??1 | ??0.06 | ??0.09 | ??1.29 | ??0.007 | ??0.002 | ??0.008 | ??0.033 | ??0.0020 | ??0.0055 | ??0.0017 | ??- | ??0.28 | ??- | ??0.21 | ??0.05 |
| ??2 | ??0.06 | ??0.33 | ??1.43 | ??0.011 | ??0.002 | ??0.008 | ??0.029 | ??0.0036 | ??0.0047 | ??0.0025 | ??- | ??0.27 | ??0.19 | ??0.22 | ??0.06 |
| ??3 | ??0.06 | ??0.29 | ??1.36 | ??0.008 | ??0.001 | ??0.007 | ??0.034 | ??0.0032 | ??0.0045 | ??0.0020 | ??- | ??0.26 | ??0.07 | ??0.21 | ??0.05 |
| ??4 | ??0.08 | ??0.27 | ??1.29 | ??0.021 | ??0.002 | ??0.003 | ??0.022 | ??0.0025 | ??0.0048 | ??0.0019 | ??- | ??0.49 | ??- | ??0.02 | ??0.02 |
| ??5 | ??0.08 | ??0.28 | ??1.02 | ??0.024 | ??0.001 | ??0.008 | ??0.027 | ??0.0010 | ??0.0039 | ??0.0016 | ??0.28 | ??0.26 | ??0.26 | ??0.16 | ??0.05 |
| ??6 | ??0.11 | ??0.22 | ??1.24 | ??0.014 | ??0.002 | ??0.009 | ??0.039 | ??0.0018 | ??0.0052 | ??0.0017 | ??- | ??0.21 | ??- | ??0.12 | ??0.04 |
| ??7 | ??0.07 | ??0.32 | ??1.41 | ??0.008 | ??0.002 | ??0.008 | ??0.037 | ??0.0005 | ??0.0043 | ??0.0012 | ??- | ??0.05 | ??- | ??0.02 | ??0.10 |
| ??8 | ??0.09 | ??0.29 | ??1.36 | ??0.019 | ??0.001 | ??0.017 | ??0.032 | ??0.0023 | ??0.0077 | ??0.0020 | ??- | ??0.26 | ??0.07 | ??0.21 | ??0.03 |
| ??9 | ??0.04 | ??0.41 | ??0.82 | ??0.006 | ??0.003 | ??0.012 | ??0.026 | ??0.0027 | ??0.0064 | ??0.0029 | ??0.44 | ??0.37 | ??0.48 | ??0.24 | ??0.03 |
| ??10 | ??0.04 | ??0.34 | ??1.16 | ??0.016 | ??0.002 | ??0.008 | ??0.044 | ??0.0048 | ??0.0056 | ??0.0033 | ??- | ??0.12 | ??- | ??0.04 | ??0.08 |
| ??11 | ??0.03 | ??0.24 | ??1.48 | ??0.011 | ??0.002 | ??0.015 | ??0.041 | ??0.0026 | ??0.0074 | ??0.0022 | ??0.29 | ??0.23 | ??0.33 | ??0.09 | ??0.04 |
| ??12 | ??0.08 | ??0.26 | ??1.59 | ??0.013 | ??0.001 | ??0.009 | ??0.032 | ??0.0023 | ??0.0047 | ??0.0016 | ??- | ??0.22 | ??- | ??0.06 | ??0.03 |
| ??13 | ??0.04 | ??0.29 | ??1.51 | ??0.007 | ??0.001 | ??0.006 | ??0.026 | ??0.0033 | ??0.0042 | ??0.0040 | ??0.16 | ??0.24 | ??0.12 | ??0.08 | ??0.05 |
| ??14 | ??0.05 | ??0.38 | ??1.46 | ??0.012 | ??0.001 | ??0.007 | ??0.046 | ??0.0029 | ??0.0044 | ??0.0018 | ??- | ??0.05 | ??- | ??0.30 | ??0.06 |
| ??15 | ? *0.13 | ??0.26 | ??1.31 | ??0.009 | ??0.001 | ??0.008 | ??0.037 | ??0.0030 | ??0.0070 | ? *0.0053 | ??- | ??0.19 | ??0.03 | ??0.09 | ??0.03 |
| ??16 | ? *0.12 | ??0.22 | ??1.36 | ??0.012 | ??0.003 | ??0.007 | ??0.028 | ??0.0026 | ??0.0038 | ??0.0027 | ??- | ??0.17 | ??0.03 | ??0.04 | ??0.04 |
| ??17 | ??0.07 | ??0.30 | ??1.25 | ??0.008 | ??0.001 | ??0.007 | ??0.035 | ??0.0034 | ??0.0036 | ? *0.0049 | ??0.04 | ??0.17 | ??0.03 | ??0.13 | ??0.04 |
| ??18 | ??0.06 | ??0.29 | ??1.36 | ??0.008 | ??0.001 | ??0.012 | ??0.042 | ? *0.0003 | ??0.0056 | ??0.0026 | ??- | ??0.14 | ??- | ??0.04 | ??0.05 |
| ??19 | ??0.05 | ??0.28 | ? *1.78 | ??0.011 | ??0.002 | ??0.008 | ??0.034 | ??0.0032 | ??0.0046 | ??0.0020 | ??- | ??0.11 | ??- | ??0.02 | ??0.05 |
| ??20 | ? *0.02 | ??0.34 | ??1.33 | ??0.016 | ??0.002 | ??0.008 | ??0.046 | ??0.0028 | ??0.0054 | ??0.0029 | ??0.28 | ??0.23 | ??0.43 | ??0.15 | ??0.03 |
| ??21 | ??0.05 | ??0.23 | ??1.36 | ??0.013 | ??0.001 | ??0.009 | ??0.039 | ? *0.0052 | ??0.0063 | ??0.0034 | ??- | ??0.16 | ??- | ??0.05 | ??0.06 |
Attention: in the table "
*" expression exceeds specialized range of the present invention
Table 2
| Steel numbering system | Steel pipe sizes | Heat-treat condition | Test result | |||||||
| Outside diameter (mm) | Wall thickness (mm) | The cooling starting temperature (℃) | Tempering temperature (℃) | ??TS ??(MPa) | ??YS ??(MPa) | Ferrite is in the crystal boundary precipitating | Microtexture | ??CAR ??(％) | ||
| The embodiment of the invention | ??1 | ??323.9 | ??40.0 | ??950 | ??650 | ??583 | ??509 | Be | ??F+B+M | ??0 |
| ??2 | ??219.1 | ??29.2 | ??950 | ??650 | ??641 | ??569 | Be | ??F+B+M | ??0 | |
| ??3 | ??219.1 | ??37.8 | ??950 | ??650 | ??602 | ??526 | Be | ??F+B+M | ??0 | |
| ??4 | ??219.1 | ??19.1 | ??950 | ??650 | ??604 | ??520 | Be | ??F+B+M | ??0 | |
| ??5 | ??323.9 | ??34.1 | ??950 | ??650 | ??605 | ??522 | Be | ??F+B+M | ??0 | |
| ??6 | ??323.9 | ??20.5 | ??950 | ??650 | ??622 | ??530 | Be | ??F+B+M | ??0 | |
| ??7 | ??323.9 | ??35.2 | ??950 | ??650 | ??618 | ??545 | Be | ??F+B+M | ??0 | |
| ??8 | ??323.9 | ??21.1 | ??950 | ??650 | ??620 | ??534 | Be | ??F+B+M | ??0 | |
| ??9 | ??219.1 | ??16.7 | ??950 | ??650 | ??584 | ??525 | Be | ??F+B+M | ??0 | |
| ??10 | ??219.1 | ??20.6 | ??950 | ??650 | ??579 | ??519 | Be | ??F+B+M | ??0 | |
| ??11 | ??219.1 | ??19.1 | ??950 | ??650 | ??588 | ??537 | Be | ??F+B+M | ??0 | |
| ??12 | ??219.1 | ??28.6 | ??950 | ??650 | ??606 | ??523 | Be | ??F+B+M | ??0 | |
| ??13 | ??219.1 | ??39.7 | ??950 | ??650 | ??584 | ??525 | Be | ??F+B+M | ??0 | |
| ??14 | ??219.1 | ??31.8 | ??950 | ??650 | ??598 | ??534 | Be | ??F+B+M | ??0 | |
| Comparing embodiment | ??15 | ??219.1 | ??28.9 | ??950 | ??650 | ??644 | ??520 | ? *Not | ??B+M | ??12.6 |
| ??16 | ??355.6 | ??23.8 | ??950 | ??650 | ??681 | ??591 | ? *Not | ??B+M | ??7.9 | |
| ??17 | ??323.9 | ??17.5 | ??950 | ??650 | ??653 | ??566 | Be | ??F+B+M | ??6.2 | |
| ??18 | ??219.1 | ??16.7 | ??950 | ??650 | ??600 | ??530 | Be | ??F+B+M | ??3.6 | |
| ??19 | ??323.9 | ??34.1 | ??950 | ??650 | ??590 | ??524 | ? *Not | ??B+M | ??10.8 | |
| ??20 | ??219.1 | ??37.8 | ??950 | ??650 | ??523 | ? *474 | Be | ??F+B | ??0 | |
| ??21 | ??323.9 | ??20.5 | ??950 | ??650 | ??585 | ??519 | Be | ??F+B+M | ??9.4 | |
Attention: the structure B shown in the table: bainite, M: martensite, F: ferrite.In the table "
*" expression exceeds specialized range of the present invention.
In comparing embodiment, the Mn content in numbering 19 the steel has exceeded prescribed value scope of the present invention, and ferrite do not exist on the interface, obtains the deteriorated result of CAR=10.8% thus.In addition, C content has exceeded prescribed value scope of the present invention in the steel of numbering 20, even therefore the excellent results of CAR=0% is arranged, can not satisfy the intensity of 5L-X70 grade.
In addition, the Ca content of the steel of numbering 21 has exceeded prescribed value of the present invention in comparing embodiment, and because inclusion causes obtaining the deteriorated result of CAR=9.4%.
(embodiment 2)
In order to confirm the effect of heat-treat condition, the steel of numbering 3 melts by converter in table 1, and will be heated to 1100 ℃ or higher by the steel billet of continuous casting production, then by using skew rolling mill to obtain hollow bloom.Finish rolling becomes steel pipe to this hollow bloom with sizing mill by mandrel mill.Steel pipe is at 920 ℃ to 20 ℃ scope internal cooling then, and produces weldless steel tube by changing cooling starting temperature, rate of cooling and tempering temperature.The size and the heat-treat condition of the steel pipe of producing are as shown in table 3.In this case, number the Ar of 3 tested steel
3Point is 768 ℃, and its Ac
1Point is 745 ℃.
As embodiment 1, the Elongation test sample of preparation JIS 12 is used for Elongation test, measures tensile strength (TS) and yield strength (YS).
In addition, anti-HIC property testing carries out under the condition identical with embodiment 1, and has measured crack area ratio (CAR (%)).In addition, after anti-HIC property testing, cut away the cross section of HIC specimen, then by its microtexture of observation by light microscope.These results are table 3 illustrate.
Table 3
| Steel numbering system | Test No. | Steel pipe sizes | Heat-treat condition | Test result | |||||||||
| Outside diameter (mm) | Wall thickness (mm) | Temperature before the even heat (℃) | The cooling starting temperature (℃) | Rate of cooling (℃/sec) | Tempering temperature (℃) | ??TS ??(MPa) | ??YS ??(MPa) | Ferrite is in the crystal boundary precipitating | Microtexture | ??CAR ??(％) | |||
| The embodiment of the invention | ??3 | ??22 | ??219.1 | ??37.8 | ??920 | ??1080 | ??30 | ??650 | ??614 | ??553 | Be | ??F+B+M | ??0 |
| ??3 | ??23 | ??219.1 | ??37.8 | ??920 | ??980 | ??30 | ??650 | ??609 | ??542 | Be | ??F+B+M | ??0 | |
| ??3 | ??24 | ??219.1 | ??37.8 | ??920 | ??900 | ??30 | ??650 | ??590 | ??513 | Be | ??F+B+M | ??0 | |
| ??3 | ??25 | ??219.1 | ??37.8 | ??920 | ??850 | ??30 | ??650 | ??564 | ??491 | Be | ??F+B+M | ??0 | |
| ??3 | ??26 | ??219.1 | ??37.8 | ??920 | ??950 | ??30 | ??650 | ??568 | ??494 | Be | ??F+B+M | ??0 | |
| ??3 | ??27 | ??219.1 | ??37.8 | ??920 | ??950 | ??30 | ??600 | ??605 | ??532 | Be | ??F+B+M | ??0 | |
| ??3 | ??28 | ??219.1 | ??37.8 | ??920 | ??950 | ??30 | ??570 | ??610 | ??537 | Be | ??F+B+M | ??0 | |
| Comparing embodiment | ??3 | ??29 | ??219.1 | ??37.8 | ??920 | ? *1150 | ??30 | ??650 | ??647 | ??589 | ? *Not | ??B+M | ? *7.4 |
| ??3 | ??30 | ??219.1 | ??37.8 | ??920 | ??950 | ??30 | ? *750 | ??521 | ? *443 | Be | ??F+B+M | ??0 | |
| ??3 | ??31 | ??219.1 | ??37.8 | ??920 | ??950 | ? *4 | ??650 | ??478 | ? *287 | Be | ? *F+P | ??0 | |
| ??3 | ??32 | ??219.1 | ??37.8 | ??920 | ? *750 | ??30 | ??650 | ??509 | ? *438 | Be | ??F+B+M | ??0 | |
| ??3 | ??33 | ??219.1 | ??37.8 | ??920 | ??950 | ??30 | ? *500 | ??642 | ??578 | Be | ??F+B+M | ??0 | |
Attention: the structure B shown in the table: bainite, M: martensite, F: ferrite, P: perlite.In the table "
*" expression exceeds specialized range of the present invention.
The result finds out from table 3, satisfies heat-treat condition given to this invention according to the steel of the test No. 22～28 of the embodiment of the invention, and all steel capital of embodiment satisfy the intensity of 5L-X70 grade, and has the excellent state of CAR=0%.
On the other hand, the steel of test No. 29 has adopted the quenching temperature that exceeds prescribed value scope of the present invention in comparing embodiment, and does not have the ferrite precipitating on crystal boundary, obtains the deteriorated result of CAR=7.4% therefrom.The steel of test No. 30 also adopts the tempering temperature that exceeds prescribed value scope of the present invention, and intensity can not satisfy the 5L-X70 grade.
In addition, in comparing embodiment, the steel of test No. 31 adopts the rate of cooling exceed prescribed value scope of the present invention, and the microtexture of steel is the ferrite-pearlite microtexture, and thus, hardness of steel can not satisfy the 5L-X70 grade.
In addition, since quenching temperature in the steel of test No. 32 less than (Ar
3Thereby hardness of steel can not satisfy the 5L-X70 grade point+50 ℃).
In addition, in comparing embodiment, the steel of test No. 33 can not be guaranteed 550 ℃ or higher tempering temperature, thereby will carry out extra welding test, and finds in the strength degradation that is subjected to welding heat affected zone.
Industrial usability
In seamless steel pipe according to the present invention and production method thereof, stipulated steel chemical composition, steel microstructure and in steel ferritic precipitating on the crystal boundary. Therefore, described steel can obtain high strength and stability, excellent anti-HIC. In addition, by the condition in the online QT situation of given application, save and improve in the situation of productivity ratio in the cost of heat treatment process or expense, the pipeline with excellent anti-HIC and 483MPa or higher high yield stress can be provided. Therefore, seamless steel pipe of the present invention and production method thereof can be widely used in the technical field that requirement has the high-strength seamless steel pipe of excellent anti-HIC.
Claims (4)
1. high-strength seamless steel pipe that excellent in hydrogen-induced cracking resistance is arranged, it is characterized in that by following elementary composition: in quality %, C:0.03-0.11%, Si:0.05-0.5%, Mn:0.8-1.6%, P:0.025% or still less, S:0.003% or still less, Ti:0.002-0.017%, Al:0.001-0.10%, Cr:0.05-0.5%, Mo:0.02-0.3%, V:0.02-0.20%, Ca:0.0005-0.005%, N:0.008% or still less and O (oxygen): 0.004% or still less, surplus is Fe and impurity, its feature is that also the microtexture of steel is bainite and/or martensite, the ferrite precipitating is to crystal boundary, and yielding stress is 483MPa or higher.
2. the described high-strength seamless steel pipe that excellent in hydrogen-induced cracking resistance is arranged of claim 1 is characterized in that also comprising, in quality %, and at least a among the Cu of 0.05-0.5% and the Ni of 0.05-0.5%.
3. production method that the high-strength seamless steel pipe of excellent in hydrogen-induced cracking resistance is arranged, the steel billet that it is characterized in that having a described composition of claim 1 becomes after the weldless steel tube, immediately with described weldless steel tube soaking, then at (Ar by hot rolling
3Point+50 ℃) under 1100 ℃ the quenching temperature with 5 ℃/second or higher rate of cooling cooling, described then weldless steel tube at 550 ℃ to Ac
1Tempering under the temperature of point, produce so a kind of weldless steel tube thus: wherein the microtexture of steel is bainite and/or martensite, the ferrite precipitating is to crystal boundary, and yielding stress is 483MPa or higher.
4. production method that has excellence that the high-strength seamless steel pipe of hydrogen-induced cracking resistance is arranged, the steel billet that it is characterized in that having a described composition of claim 2 becomes after the weldless steel tube, immediately with described weldless steel tube soaking, then at (Ar by hot rolling
3Point+50 ℃) under 1100 ℃ the quenching temperature with 5 ℃/second or higher rate of cooling cooling, then with described weldless steel tube at 550 ℃ to Ac
1Tempering under the temperature of point, produce so a kind of weldless steel tube thus: the microtexture of steel is bainite and/or martensite, the ferrite precipitating is to crystal boundary, and yielding stress is 483MPa or higher.
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