CN1875121A - High strength stainless steel pipe for line pipe excellent in corrosion resistance and method for production thereof - Google Patents
High strength stainless steel pipe for line pipe excellent in corrosion resistance and method for production thereof Download PDFInfo
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- 239000010935 stainless steel Substances 0.000 title claims abstract description 74
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- 238000005260 corrosion Methods 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 40
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- 238000001816 cooling Methods 0.000 claims description 101
- 238000003466 welding Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 33
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- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000007858 starting material Substances 0.000 claims description 11
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Abstract
Provided is a high strength stainless steel pipe for a line pipe excellent in corrosion resistance, which has a chemical composition, in mass %, that C: 0.001 to 0.015 %, Si: 0.01 to 0.5 %, Mn: 0.1 to 1.8 %, P: 0.03 % or less, S: 0.005 % or less, Cr: 15 to 18 %, Ni: 0.5 % or more and less than 5.5 %, Mo: 0.5 to 3.5 %, V: 0.02 to 0.2 %, N: 0.001 to 0.015 %, O: 0.006 % or less, with the proviso that C + 0.65Ni + 0.6Mo - 20C >= 18.5, Cr + Mo + 0.3Si - 43.5C - 0.4Mn - Ni - 0.3Cu - 9N >= 11.5 and C + N <= 0.025 are satisfied. Preferably, the pipe is subjected to a quenching-tempering treatment. The steel pipe may further contain 0.002 to 0.05 % of Al. It may further contain one or more selected from among Nb, Ti, Zr, B and W, and/or, Cu or Ca. The steel pipe preferably has a structure containing martensite, ferrite and retained gamma.
Description
Technical field
The present invention relates to the steel pipe that uses in the pipeline of a kind of crude oil of carrying oil well or gas well production or Sweet natural gas.Be particularly related to a kind of suitable conveying and contain carbon dioxide (CO
2), chlorion (Cl
-) wait the oil well under the unusual heavy corrosion environment, crude oil or the Sweet natural gas high strength stainless steel pipe and the manufacture method thereof that use, that have superior corrosion resistance and the crackle of anti-sulphide stress corrosion property of gas well production.In addition, so-called in the present invention " high strength stainless steel pipe " is meant to have yield strength: the stainless steel tube of the above intensity of 413MPa (60ksi).
Background technology
In recent years, for the exhaustion of the rise of tackling crude oil price and the petroleum resources envisioned in the near future, for cost was high deep layer oil field in the past with in case the exploitation in the stronger acidifying gas field of the corrodibility that exploitation is just abandoned etc. is just worldwide in vogue.Such oil field, gas field generally are very dark, and its atmosphere also is the condition of high temperature, and for containing CO
2, Cl
-Etc. serious corrosive environment.Thereby, transport so employed line pipe of the crude oil that oil field, gas field produced, Sweet natural gas, require the material of steel pipe to have higher intensity and toughness and have superior corrosion resistance.In addition, the exploitation of marine oil field also enlivens, considers from the viewpoint that reduces the pipeline installation cost, requires employed steel pipe also to possess good weldability.
In the past, as the material of line pipe, from containing CO
2, Cl
-Environment under the viewpoint of weldability consider, use carbon steel, carry out protection against corrosion by adding inhibitor., inhibitor has under the condition of high temperature effect relatively poor, and can cause the problem of environmental pollution etc., has to suppress the trend used.In addition, a part of line pipe uses the two phase stainless steel pipe., although two phase stainless steel pipe good corrosion resistance, the alloying element amount is more, and hot workability is relatively poor, can only have its problem of ultra-high price with special thermal processing method manufacturing.For this reason, its use has the tendency that is restricted.From such problem, more wish the steel pipe of cheap, weldability and excellent corrosion resistance.
For such requirement, the stainless pipe of martensite that for example proposes to have improved the 11%Cr of weldability or 12%Cr in patent documentation 1, patent documentation 2, patent documentation 3 is as line-pipes.
The steel pipe of patent documentation 1 record is the line-pipes martensite stainless steel pipe that has suppressed the hardness excellent corrosion resistance that rise, weld part of weld part owing to low carbonization.In addition, the steel pipe of patent documentation 2 records is by adjusting the alloying element amount, having improved the martensite stainless steel pipe of erosion resistance.The steel pipe of patent documentation 3 records is line-pipes martensite stainless steel pipes that weldability and erosion resistance are satisfied simultaneously.
Patent documentation 1: the spy opens flat 08-41599 communique
Patent documentation 2: the spy opens flat 09-228001 communique
Patent documentation 3: the spy opens flat 09-316611 communique
Summary of the invention
Yet under the high environment of hydrogen sulfide sectional pressure, there are the situation that the sulphide stress corrosion crackle takes place in 11% or 12%Cr martensite stainless steel pipe with the technology of being put down in writing in patent documentation 1, patent documentation 2, the patent documentation 3 is made, and are containing CO
2, Cl
-Deng, surpassing under 150 ℃ of pyritous environment, existence can not stably show the problem of the erosion resistance of expectation.
The present invention is based on that in the past technical situation finishes.Its purpose is to provide a kind of high strength stainless steel pipe for line pipe and manufacture method thereof, and this steel pipe cheapness is even containing CO
2, Cl
-Under the harsh corrosive environment of pyritous more than 150 ℃, also demonstrate good anti-CO
2Corrodibility.And, even under the environment of high hydrogen sulfide, also demonstrate good resistance to sulfide stress cracking, and have good low-temperature flexibility and good weldability concurrently.
The present inventor is for finishing above-mentioned problem, and the composition of the 12%Cr steel of representational martensite stainless steel pipe as substrate, is being contained CO to relating to
2, Cl
-Deng high-temperature corrosion environment under erosion resistance, the influence of various factors of the crackle of anti-sulphide stress corrosion property under the high hydrogen sulfide environment, carried out wholwe-hearted repeatedly research.It found that, in the martensite stainless steel pipe of 12%Cr, formation rolls up Cr, compare simultaneously C, N were significantly reduced, and the composition that contains Cr, Ni, Mo or Cu in right amount, and tissue is become martensitic phase as basic phase, contain ferritic phase and residual austenite tissue mutually, can guarantee that yield strength is the above high strength of 413Mpa (60ksi), good hot workability and erosion resistance under harsh environment and better weldability, until having finished the present invention.
At first, the content that the present inventor studied is elaborated.
Aspect in the past manufacturing martensitic stainless steel weldless steel tube, generating ferritic phase, it is organized not under the monophasic situation of martensite, because its intensity reduces, hot workability reduces, and it is generally acknowledged in the manufacturing of steel pipe and has any problem.
Therefore, the present inventor has further carried out detailed research to relating to the influence of hot workability composition.It found that: make it satisfy following (2) formula by adjusting the steel pipe composition, hot workability obviously improves, and crackle takes place in the time of can preventing hot-work.
Cr+Mo+0.3Si-43.5C-Ni-0.3Cu-9N≥11.5 …(2)
(wherein, Cr, Ni, Mo, Cu, C, Si, Mn, N are the content (quality %) of each element)
The relation table of the crack length that (, when making weldless steel tube) takes place at the end face of 13%Cr class stainless-steel seamless pipe during with the value on (2) formula left side, with hot-work is shown in Fig. 1.As can be seen from Figure 1, the value on (2) formula left side is 8.0 when following, and perhaps the value on (2) formula left side can prevent crackle more than 11.5, preferred 12.0 when above.(2) value on the formula left side is equivalent to not produce fully ferritic zone 8.0 when following, this zone be do not generate ferritic phase think the zone of improving hot workability in the past.On the other hand, along with (2) formula left side value becomes big, the ferritic amount of generation increases, and the value on (2) formula left side is the ferritic zone of more generation in the zone more than 11.5.That is, the present inventor finds for the first time, adjust and form so that (2) formula left side value is more than 11.5, the tissue of the more generation of ferrite when forming tubulation, by adopting this and diverse viewpoint in the past, can make hot workability be improved significantly.
During hot-work, the crack length that takes place at the end face of 13%Cr class stainless-steel seamless pipe is shown among Fig. 2 with the sorting table that concerns of itself and ferrite content.As can be seen from Figure 2, according to viewpoint in the past, ferritic amount is counted at 0% o'clock with volume percent crackle is not taken place, but generate ferrite crackle takes place simultaneously., further increase and generate ferritic amount, make its volume fraction more than 10%, different when preferably generating the ferritic phase more than 15% with in the past viewpoint, can prevent crackle.That is, adjust its composition, generate the ferritic phase of proper range, form ferrite-martensitic two phase constitutions, can improve hot workability thus, prevent the generation of crackle to satisfy formula (2).
, adjust its composition and satisfy (2) formula, when its tissue becomes ferrite-martensitic two phase constitutions, then worry to make its erosion resistance deterioration in thermal treatment because the element that produces distributes.When becoming two-phase and organize, the austenite generting element of C, Ni, Cu etc. is spread in the martensitic phase, and the ferrite generting element of Cr, Mo etc. is spread in the ferritic phase, in the finished product after the thermal treatment, as a result of, the deviation of composition takes place between mutually at each.In the martensitic phase the effective Cr amount of erosion resistance is reduced, the C amount of erosion resistance deterioration is increased, probably compare its heterochromia and reduce with uniform formation.
So the present inventor studies the influence of erosion resistance with regard to composition.It found that: by adjusting its composition following to satisfy (1) formula, even its tissue becomes ferrite-martensitic two phase constitutions, also can guarantee its sufficient erosion resistance.
Cr+0.65Ni+0.6Mo+0.55Cu-20C≥18.5 …(1)
(wherein, Cr, Ni, Mo, Cu, C are the content (quality %) of each element)
With the value on (1) formula left side, with contain CO
2And Cl
-200 ℃ hot environment under the relation table of corrosion speed be shown in Fig. 3.As can be seen from Figure 3, satisfy formula (1), be organized as ferrite-martensitic two phase constitutions, containing CO even make by adjusting its composition
2And Cl
-200 ℃ hot environment under, also can guarantee its sufficient erosion resistance.
As seen from formula (1), be the raising erosion resistance, the content that increases Cr is effective., Cr promotes ferritic generation.Therefore, suppress to generate ferritic purpose, needed to contain and the matched Ni amount of Cr content in the past for reaching., when the Ni constituent content being increased when the amount that cooperates the Cr element, austenite phase stabilization then, existence can not guarantee that line-pipes steel tube place needs the problem of intensity.
For this problem, the present inventor has carried out further research, found that, by under the state of the ferrite of keeping the ferritic phase that contains appropriate amount-martensitic two phase constitutions, increase Cr content, the residual quantity of austenite phase can be suppressed lower, can guarantee full intensity as the line-pipes steel pipe.
The present inventor after with the thermal treatment of resulting 13%Cr class stainless-steel seamless pipe with ferrite-martensite two phase constitutions yield strength YS and the relation of Cr content, be shown in Fig. 4.And, in Fig. 4, also write down the YS after the thermal treatment and the relation of Cr content when being organized as single-phase or martensite-austenite two phase constitutions of martensite simultaneously.Obtain latest find by Fig. 4,, increase the content of Cr, can guarantee line-pipes steel pipe full intensity by tissue being maintained comprise ferrite-martensite two phase constitutions of the ferritic phase of appropriate amount.On the other hand, make when being organized as single-phase or martensite-austenite two phase constitutions of martensite, when increasing Cr content, YS then reduces.
In addition, the line-pipes steel pipe is implemented the circumference welding when the pipeline installation pipe.The circumference welding is different with the thermal treatment of tube body, uses the mode of the little part heating of heat, and speed of cooling is fast, and heat affected zone obviously hardens.When heat affected zone hardens, then relevant with the generation welding crack.So, the influence of welding crack when welding circumference, composition takes place, studies, and it found that, satisfies (3) formula down by the composition of adjusting steel pipe,
C+N≤0.025 ……(3)
Can welding crack not take place, guarantee good weldability.Relation with the cracking frequency in the welding crack experiment of the value on (3) formula left side and Y shape slit is illustrated among Fig. 5.Find from Fig. 5, become below 0.025, can prevent welding crack by the value that makes (3) formula left side.The incidence of crackle is tried to achieve by crackle number/test number from the welding crack experiment of implementing each 5 Y shape slit.
The present invention is based on above-mentioned opinion, has carried out wholwe-hearted research and has obtained.That is, main points of the present invention are as follows:
(1) high strength stainless steel pipe for line pipe of excellent corrosion resistance is characterized in that, it has
% contains in quality
C：0.001～0.015％ Si：0.01～0.5％
Mn:0.1～below 1.8% P:0.03%
The following Cr:15 of S:0.005%～18%
Above and less than 5.5% Mo:0.5～3.5% of Ni:0.5%
V：0.02～0.2％ N：0.001～0.015％
Below the O:0.006%
So that satisfy following (1), (2) and (3) formula, surplus is Fe and unavoidable impurities
Composition,
Cr+0.65Ni+0.6Mo+0.55Cu-20C≥18.5 …(1)
Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5…(2)
C+N≤0.025 …(3)
Wherein, C, Ni, Mo, Cr, Si, Mn, Cu, N represent the content (quality %) of each element.
(2) as (1) described high strength stainless steel pipe for line pipe, it is characterized in that except that above-mentioned composition, also having the composition that contains Al:0.002～0.05% in quality %.
As (1) or (2) described high strength stainless steel pipe for line pipe, it is characterized in that (3) in quality %, the content of described Ni is 1.5～5.0%.
As each described high strength stainless steel pipe for line pipe in (1)～(3), it is characterized in that (4) in quality %, the content of described Mo is 1.0～3.5%.
As each described high strength stainless steel pipe for line pipe in (1)～(3), it is characterized in that (5) in quality %, the content of described Mo is greater than 2% and is no more than 3.5%.
(6) as each described high strength stainless steel pipe for line pipe in (1)～(5), it is characterized in that except that above-mentioned composition, also having in quality % and contain composition below the Cu:3.5%.
As (6) described high strength stainless steel pipe for line pipe, it is characterized in that (7) in quality %, the content of described Cu is 0.5%～1.14%.
(8) as each described high strength stainless steel pipe for line pipe in (1)～(7), it is characterized in that, except that above-mentioned composition, also have in quality % and contain the composition more than a kind or 2 kinds that is selected from below the Nb:0.2%, below the Ti:0.3%, below the Zr:0.2%, below the B:0.01% and in below the W:3.0%.
(9) as each described high strength stainless steel pipe for line pipe in (1)～(8), it is characterized in that except that above-mentioned composition, also having in quality % and contain composition below the Ca:0.01%.
(10) as each described high strength stainless steel pipe for line pipe in (1)～(9), it is characterized in that, except that above-mentioned composition, also have with martensitic phase as basic phase, in volume ratio contain below 40% retained austenite mutually and the tissue of 10～60% ferritic phase.
As (10) described high strength stainless steel pipe for line pipe, it is characterized in that (11) described ferritic phase counts 15～50% with volume ratio.
(12) as (10) or (11) described high strength stainless steel pipe for line pipe, it is characterized in that described retained austenite is counted below 30% with volume ratio.
(13) manufacture method of the high strength stainless steel pipe for line pipe of excellent corrosion resistance is characterized in that, will have
Contain
C：0.001～0.015％ Si：0.01～0.5％
Mn:0.1～below 1.8% P:0.03%
The following Cr:15 of S:0.005%～18%
Above and less than 5.5% Mo:0.5～3.5% of Ni:0.5%
V：0.02～0.2％ N：0.001～0.015％
Below the O:0.006%
So that satisfy following (1), (2) and (3) formula, surplus is Fe and unavoidable impurities
The steel pipe starting material of composition, make the steel pipe of specified dimension, with the temperature more than this steel pipe reheat to 850 ℃, be cooled to below 100 ℃ with the above speed of cooling of air cooling speed then, then, implement to be heated to the quenching-temper of the temperature below 700 ℃
Cr+0.65Ni+0.6Mo+0.55Cu-20C≥18.5 …(1)
Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5…(2)
C+N≤0.025 …(3)
Wherein, Cr, Ni, Mo, Cu, C, Si, Mn, N represent the content (quality %) of each element.
(14) as the manufacture method of (13) described high strength stainless steel pipe for line pipe, it is characterized in that, described steel pipe starting material are heated, by the hot-work tubulation, behind the tubulation, be cooled to room temperature with the speed of cooling more than the air cooling speed, make the weldless steel tube of specified dimension, then this weldless steel tube is implemented described quenching-temper.
(15) as the manufacture method of (13) or (14) described high strength stainless steel pipe for line pipe, it is characterized in that, replace described quenching-temper, implement to be heated to the temper of the temperature below 700 ℃.
(16) as the manufacture method of each described high strength stainless steel pipe for line pipe in (13)～(15), it is characterized in that, remove above-mentioned composition part, have the composition that contains Al:0.002～0.05% in quality %.
As the manufacture method of each described high strength stainless steel pipe for line pipe in (13)～(16), it is characterized in that (17) in quality %, the content of described Ni is 1.5～5.0%.
(18) as (manufacture method of each described high strength stainless steel pipe for line pipe is characterized in that in 13～(17), and in quality %, the content of described Mo is 1.0～3.5%.
As the manufacture method of each described high strength stainless steel pipe for line pipe in (13)～(17), it is characterized in that (19) in quality %, the content of described Mo is greater than 2% and is no more than 3.5%.
(20) as the manufacture method of each described high strength stainless steel pipe for line pipe in (13)～(19), it is characterized in that except that above-mentioned composition, % also contains below the Cu:3.5% in quality.
As the manufacture method of (20) described high strength stainless steel pipe for line pipe, it is characterized in that (21) in quality %, the content of described Cu is 0.5%～1.14%.
(22) as the manufacture method of each described high strength stainless steel pipe for line pipe in (13)～(21), it is characterized in that, except that above-mentioned composition, also contain in quality % be selected from below the Nb:0.2%, below the Ti:0.3%, below the Zr:0.2%, below the W:3% and in below the B:0.01% more than a kind or 2 kinds.
(23) as the manufacture method of each described high strength stainless steel pipe for line pipe in (13)～(22), it is characterized in that except that above-mentioned composition, % also contains below the Ca:0.01% in quality.
(24) welding structure thing, it is by forming each described high strength stainless steel pipe welded joint in (1)～(12).
Description of drawings
Fig. 1 is the chart of the influence of the crack length that takes place when forming hot-work of expression steel plate.
The chart of crack length that Fig. 2 takes place when being expression hot-work and ferrite content relation.
Fig. 3 is illustrated in to contain CO
2And Cl
-200 ℃ hot environment under, steel plate is formed the chart to the influence of corrosion speed.
Fig. 4 be expression after the thermal treatment yield strength YS and the chart of Cr relation with contents.
Fig. 5 is the chart of the amount of expression (C+N) to the influence of the welding crack incidence in the welding crack experiment of Y shape slit.
Embodiment
At first, the qualification basis that the high strength stainless steel pipe for line pipe that limits among the present invention is formed describes.Below, the quality % in the composition only remembers and makes %.
C：0.001～0.015％
C is the important element relevant with martensitic stainless steel intensity, needs to make it to contain more than 0.001% among the present invention, when content for a long time, the sensitization when causing the tempering that contained Ni causes easily.Sensitization when preventing this tempering is made as 0.015% with the upper limit of C.Thereby the amount that limits the C element in the present invention is in 0.001～0.015% scope.Consider that from the viewpoint of erosion resistance, weldability preferred C element must lack as far as possible, and preferred 0.002～0.01 scope.
Si：0.01～0.5％
Si has been the element of reductor effect, is essential element in the manufacturing processed of steel generally, must contain more than 0.01%, contains to surpass 0.5% then anti-CO
2Corrodibility reduces, and hot workability is reduced.Therefore, limit Si in 0.01～0.5% scope.
Mn：0.1～1.8％
Mn is the element that its intensity is increased, and for guaranteeing desired intensity, it is contained more than 0.1% in the present invention, but when surpassing 1.8%, then makes its toughness be subjected to bad influence.Limit Mn in 0.1～1.8% scope for this reason.And preferred 0.2～0.9%.
Below the P:0.03%
P makes anti-CO
2Corrodibility, anti-CO
2Stress corrosion cracking, anti-pitting attack and the crackle of anti-sulfide corrosion property be the element of deterioration together.Wish that in the present invention it reduces as far as possible, and extreme reduction can cause manufacturing cost to rise.P is chosen to be below 0.03%, and this scope is the industrial less expensive and scope that may implement, and does not make anti-CO
2Corrodibility, anti-CO
2Stress corrosion cracking, anti-pitting attack and the crackle of anti-sulphide stress corrosion property be the scope of deterioration together.Preferred in addition its below 0.02%.
Below the S:0.005%
S is in the manufacturing processed of steel pipe, makes the element of the obvious deterioration of its hot workability, wishes that it must lack as far as possible, can make steel pipe if be reduced to 0.005% with conventional operation with next, therefore set S on be limited to 0.005%.Preferred in addition below 0.003%.
Cr：15～18％
Cr is the element that forms the protection tunicle, improves erosion resistance, particularly helps to improve anti-CO
2Corrodibility, anti-CO
2The effective element of stress corrosion cracking.In the present invention, from improving the viewpoint of the erosion resistance under the harsh and unforgiving environments, need it to contain more than 15% especially.On the other hand, when its content surpasses 18%, the hot workability deterioration.Therefore, Cr is limited to 15～18% scope.
Ni:0.5% is above, less than 5.5%
The Ni element makes high Cr steel protection tunicle firm, has the raising erosion resistance, makes the effect of the intensity increase of low C high Cr steel simultaneously.In the present invention, need contain more than 0.5%, but when containing 5.5% when above, hot workability reduces, cause its intensity to reduce simultaneously.Therefore, Ni is limited to more than 0.5%, in the scope of less than 5.5%.Preferred in addition 1.5%～5.0%.
Mo：0.5～3.5％
Mo increases Cl
-The resistivity of pitting attack element, need in the present invention to contain more than 0.5%.During Mo less than 0.5%, the erosion resistance under the hot environment is insufficient.On the other hand, its content surpasses at 3.5% o'clock, and erosion resistance and hot workability reduce, and manufacturing cost increases simultaneously.Therefore, Mo is limited in 0.5～3.5% the scope.And preferred 1.0～3.5%, more preferably surpass 2% and below 3.5%.
V：0.02～0.2％
V has the intensity of making and increases, and improves the effect of anticorrosion stress-resistant crackle simultaneously.This effect is 0.02% more obvious when above at its content, but when surpassing 0.2%, toughness is deterioration then.Therefore, V is limited in 0.02～0.2% the scope.Preferred 0.02～0.08%.
N：0.001～0.15％
N is the element that makes the obvious deterioration of weldability, preferably reduces as much as possible.Because its excessive reduction can cause the rising of manufacturing cost, so establish 0.001% as lower limit.Its amount surpasses at 0.015% o'clock, the circumference welding crack might take place, so in the present invention with 0.015% upper limit as N.
Below the O:0.006%
Existence makes various characteristics be subjected to bigger influence to O as oxide compound in steel, so its content is low more good more.When O content is more when surpassing 0.006%, hot workability, anti-CO
2Stress corrosion cracking, anti-pitting attack and the crackle of anti-sulphide stress corrosion property and toughness all obviously reduce.Therefore, in the present invention O is limited to below 0.006%.
Among the present invention, outside above-mentioned essentially consist, can also contain Al:0.002～0.05%.Al is the element with very strong desoxydatoin, preferably contain more than 0.002%, but its content surpasses at 0.05% o'clock, and toughness is brought detrimentally affect.For this reason, preferred Al is limited to 0.002～0.05% scope.In addition, more preferably below 0.03%.In addition, when not adding Al, it allows content less than 0.002% degree as unavoidable impurities.If Al is limited in less than 0.002% degree, then has the advantage that low-temperature flexibility, anti-pitting attack are improved significantly.
And, outside above-mentioned each composition, can also contain the Cu below 3.5% among the present invention.Cu makes the protection tunicle firm, suppresses hydrogen and enters in the steel, improves the element of the crackle of anti-sulphide stress corrosion property.For obtaining such effect, it is contained more than 0.5%.On the other hand, content surpasses at 3.5% o'clock, causes the crystal boundary of CuS to be separated out, and hot workability reduces.Therefore, preferably Cu is limited to below 3.5%.And more preferably 0.5～1.14%.
In addition, outside above-mentioned various compositions, can also contain and be selected from below the Nb:0.2% among the present invention, below the Ti:0.3%, below the Zr:0.2%, below the B:0.01%, during W:3.0% is following more than a kind or 2 kinds.
Nb, Ti, Zr, B, W have the effect that the intensity of making increases, and can select as required, contain more than a kind or 2 kinds.
Nb forms carbonitride, gains in strength, and helps to improve the flexible element.For obtaining such effect, it is contained more than 0.02%, and its content surpass at 0.2% o'clock, its toughness is reduced.Thereby preferably the content with the Nb element is limited to below 0.2%.
Ti, Zr, B, W also are when gaining in strength, and have the element that improves the effect of anticorrosion stress-resistant crackle.This effect is containing more than the Ti:0.02%, and is remarkable when W:0.25% is above more than the B:0.0005% more than the Zr:0.02%, exceeds following content Ti:0.3% respectively but work as each element, Zr:0.2%, and B:0.01%, during W:3.0%, the toughness deterioration.Therefore, preferably be defined as below the Ti:0.3%, below the Zr:0.2%, below the B:0.01%, below the W:3.0%.
And, among the present invention, outside above-mentioned each composition, can also contain below the Ca:0.01%.Ca fixes S as CaS, has the effect that makes sulfide-based inclusion balling, and the lattice deformability of inclusion matrix is on every side reduced, and has the hydrogen capture that makes inclusion and can reduce effect, can determine its content as required.For obtaining this effect, its content is preferred more than 0.0005%, but its content surpasses at 0.01% o'clock, causes CaO to increase anti-CO
2Corrodibility, anti-pitting attack reduction.Therefore, preferred Ca is limited to the scope below 0.01%.And more preferably 0.0005～0.005% scope.
Surplus beyond the mentioned component is Fe and unavoidable impurities.
Among the present invention, contain the composition of above-mentioned scope, and (1)～(3) formula below satisfying.
Cr+0.65Ni+0.6Mo+0.55Cu-20C≥18.5 …(1)
Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5…(2)
C+N≤0.025 …(3)
(wherein, Cr, Ni, Mo, Cu, C, Si, Mn, N are the content (quality %) of each element)
In addition, the element that does not contain in the formula calculates by zero %.
Cr+0.65Ni+0.6Mo+0.55Cu-20C≥18.5 …(1)
(1) left side of formula is an index of estimating erosion resistance, during the value less than 18.5 on (1) formula left side, is containing CO
2, Cl
-The serious corrosive atmosphere of pyritous under and under the environment of high hydrogen sulfide, do not demonstrate desired erosion resistance.Thereby in the present invention, the content of adjustment Cr, Ni, Mo, Cu, C is in above-mentioned scope and make it satisfy (1) formula.And the value on preferred (1) formula left side is more than 20.0.
Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 …(2)
(2) left side of formula is an index of estimating hot workability, and in the present invention, the content of adjustment Cr, Mo, Si, C, Ni, Mn, Cu, N is in above-mentioned scope and make it satisfy (2) formula.(2) during the value less than 11.5 on the formula left side, ferritic phase can not fully be separated out, and the hot workability deficiency is had any problem in the manufacturing of weldless steel tube.In the present invention, be improved, obviously reduce the content of P, S, O, but just reduce the content of P, S, O respectively, can not guarantee sufficient hot workability aspect the manufacturing martensitic stainless steel weldless steel tube for making hot workability.In order to ensure making the needed sufficient hot workability of weldless steel tube, importantly on the basis of the content that obviously reduces P, S, O, adjust the content of Cr, Mo, Si, C, Ni, Mn, Cu, N, make it satisfy (2) formula.And from the viewpoint that hot workability improves, the value on (2) formula left side is preferably more than 12.0.
C+N≤0.025 ……………………… (3)
(3) left side of formula is an index of estimating weldability, when the value on (3) formula left side surpasses 0.025, welding crack takes place then morely.Thereby the present invention adjusts C, N makes it satisfy (3) formula.
High strength stainless steel pipe for line pipe of the present invention, outside above-mentioned composition, preferably have tissue as described below: with martensitic phase as basic phase, the volume fraction meter, contain below 40%, the more preferably residual austenite below 30% and 10～60%, more preferably 15～50% ferritic phase.In addition, so-called martensitic phase also comprises the tempered martensite phase among the present invention.By with martensitic phase as basic phase, can make high-intensity stainless steel tube.And martensitic phase preferably contains more than 25% in volume fraction.And ferritic phase is the tissue that soft processibility is improved, and among the present invention, preferably contains more than 10% in volume fraction.On the other hand, when the ferritic phase volume fraction surpasses 60%, be difficult to guarantee desired high strength.So ferritic phase is preferably 10～60% in volume fraction.And, more preferably 15～50%.In addition, residual austenite is to improve the flexible tissue mutually, but when its volume fraction surpasses 40%, then is difficult to guarantee desired high strength.Therefore, the volume fraction of residual austenite phase is preferably below 40%, and the volume fraction of residual austenite phase is more preferably below 30%.
Below, to the manufacture method of the preferred high strength stainless steel pipe for line pipe of the present invention, be that example describes with the weldless steel tube.
At first, preferably to having the molten steel of above-mentioned composition, carry out melting with the generally well-known melting method of converter, electric furnace, vacuum melting stove etc., use Continuous casting process, ingot casting-generally well-known methods such as cogging steel rolling method is made the steel pipe starting material of billet etc.Then, these steel pipe starting material heating, with common Mannesmann-plug plug rolling mode or with the manufacturing process of the seamless tube rolling mode of Mannesmann-plug, make steel pipe by hot-work, obtain the weldless steel tube of specified dimension, the weldless steel tube behind the tubulation is above with air cooling, preferably be speed of cooling cool to room temperature more than the 0.5 ℃/s with the average cooling rate between 800～500 ℃.
So long as the weldless steel tube of the composition in the invention described above scope, after hot-work, more than air cooling, be the above speed of cooling cool to room temperature of 0.5 ℃/s preferably with the average cooling rate between 800～500 ℃, just can form with the tissue of martensitic phase as basic phase.After hot-work (tubulation), with more than the air cooling, be that the above speed of cooling of 0.5 ℃/s is carried out refrigerative and handled and get final product preferably, in the present invention also preferably and then execution quenching-temper with the average cooling rate between 800～500 ℃.
Quench treatment, be preferably processing as described below: more than the reheat to 850 ℃, keep its temperature 10min above after, with more than the air cooling, be that the speed of cooling of 0.5 ℃/s is cooled to below 100 ℃ preferred cool to room temperature preferably with the average cooling rate between 800～500 ℃.If quenching temperature is less than 850 ℃, and its tissue can not become sufficient martensitic stucture, and its intensity has the tendency of reduction.Thereby the reheat temperature of quench treatment preferably is limited to the temperature more than 850 ℃.In addition, the speed of cooling behind the reheat, if less than air cooling speed, between 800～500 ℃ average 0.5 ℃/s of less than, its tissue can not become sufficient martensitic stucture.For this reason, the speed of cooling behind the reheat preferably sets more than the air cooling, and the average cooling rate between 800～500 ℃ is the above speed of cooling of 0.5 ℃/s.
As temper, be preferably as follows described processing: after implementing quench treatment, then be heated to the temperature below 700 ℃.By be heated to below 700 ℃, preferred temperature more than 400 ℃ carries out tempering, its tissue forms the tissue that contains tempered martensite phase, residual austenite phase, ferritic phase, becomes to have desired high strength and the desired high tenacity and the weldless steel tube of desired superior corrosion resistance.And, after preferably being heated to said temperature and keeping, with the above speed of cooling cooling of air cooling by time of defined.
And, replace above-mentioned quenching-temper, can only implement be heated to below 700 ℃, preferred temperature more than 400 ℃, carry out the tempered temper.
So far, be to be the explanation that example is carried out with the weldless steel tube, steel pipe of the present invention is not limited thereto.Use has the steel pipe starting material of the composition in the invention described above scope, according to common operation, also can make Electric Welded Steel Pipe, UOE steel pipe as the line-pipes steel pipe.
In addition, even in the steel pipe of Electric Welded Steel Pipe, UOE steel pipe etc., also, implement above-mentioned quenching-temper preferably to making the steel pipe behind the pipe.Can make it become welded structure by welded joint high-strength stainless steel steel pipe of the present invention.Welded structure for example has line pipe, well casing etc.And, in the welded structure described herein, the joint between the high strength stainless steel pipe of the present invention is arranged not only, also comprise the joint of the steel pipe of high strength stainless steel pipe of the present invention and other kinds in addition.
Be to illustrate in greater detail the present invention below according to embodiment.
Embodiment
Embodiment 1
Behind the liquid steel degassing of forming shown in the table 1, the steel ingot of casting 100kgf is as the steel pipe starting material.Then with these steel pipe starting material, utilize the seamless milling train of model by the hot-work tubulation, it is cold to make the laggard line space of steel pipe, makes the weldless steel tube of external diameter 3.3in * wall thickness 0.5in.
To the weldless steel tube that obtains, under the state of air cooling behind the tubulation, surfaces externally and internally is investigated in range estimation flawless generation, estimates hot workability.When there is crackle more than the long 5mm in the steel pipe front/rear end, be defined as crackle, be defined as flawless in addition.
In addition, to the weldless steel tube that obtains, under the conditions shown in Table 2, after the heating of quenching keeps, quench.Implement the temper of condition shown in the table 2 again.
Take the structure observation sample from the weldless steel tube that obtains, structure observation is passed through the KOH electrolytic corrosion with sample,, more than 50 visuals field tissue is made a video recording with scanning electronic microscope (400 times), use image analysis apparatus to calculate the tissue branch rate (volume %) of ferritic phase.In addition, the tissue branch rate of residual austenite phase is taked the mensuration sample from the weldless steel tube that obtains, and adopts X-ray diffraction method to measure.Measure the diffraction X ray integrated intensity of (211) face of (220) face, the α of γ by X-ray diffraction, convert with following formula.
γ (volume %)=100/{1+ (I α R γ/I γ R α) }
Wherein, the integrated intensity of I α: α
The integrated intensity of I γ: γ
The crystallography calculated value of R α: α
The crystallography calculated value of R γ: γ
In addition, the tissue branch rate of martensitic phase calculates as the surplus beyond these phases.
And, from the weldless steel tube that obtains, take API arc tension specimen, implement tension test, obtain tensile properties (yield strength YS, tensile strength TS).
In addition, to the weldless steel tube that obtains, the welding material shown in the table 4 is used in the end of similar steel pipe against each other, makes the seam of welded tube under the welding conditions shown in the table 4.
For the welded tube seam that obtains, range estimation is investigated and is had or not the generation welding crack.
Further, take sample, implement toughness of welded zone test, weld part corrosion test, weld part pitting attack experiment, the experiment of weld part sulphide stress corrosion crackle from the welded tube seam that obtains.Experimental technique is as follows:
(1) toughness of welded zone experiment
On the welded tube seam that obtains,, take according to the regulation of JIS Z 2242 with the V-notch sample (thickness: 5mm), implement Charpy impact test, ask the absorption energy vE in the time of-60 ℃ of gap position as welding heat affected zone according to the regulation of JIS Z 2202
-60(J), estimate the toughness of welding heat affected zone.
(2) weld part corrosion test
On the welded tube seam that obtains, take the corrosion sample of thick 3mm * wide 30mm * long 40mm by mechanical workout, contain welding metal, welding heat affected zone and mother metal portion on it.Corrosion test is the experimental liquid in remaining in autoclave: 20% the NaCl aqueous solution (liquid temperature: the CO under 200 ℃, 50 normal atmosphere
2In the gas atmosphere) in, the immersion corrosion sample was 2 weeks between soak period.For the sample after the corrosion test, gravimetry according to the reduction of the weight before and after the corrosion test, is obtained the corrosion speed of calculating.
(3) pitting corrosion test of weld part
On the welded tube seam that obtains, take sample by mechanical workout, contain welding metal, welding heat affected zone and mother metal portion on it.Pitting corrosion test is sample to be soaked in 40% CaCl
2In (liquid temperature: 70 ℃) solution, kept 24 hours.After the test, be that 10 times magnifying glass view-point corrosion has or not with multiplying power.To not have the pitting attack note and do zero, do there being pitting attack to remember *, estimate.And, be defined as pitting attack observing the pitting attack of diameter more than 0.2mm, in addition be defined as no pitting attack.
(4) weld part sulphide stress corrosion crack test
On the welded tube seam that obtains, decide loading type sample by what mechanical workout was taked NACE-TM 0177Method A regulation, contain welding metal, welding heat affected zone and mother metal portion on it.The sulphide stress corrosion crack test is that sample is remained on the experimental liquid that remains in the autoclave: the 20%NaCl aqueous solution (pH:4.0, H
2The S dividing potential drop: 0.005MPa), with additional stress as the mother metal yielding stress 90%, be 72h between effective date.To have crackle that note takes place to do *, note takes place and does zero and estimate in flawless.Gained is the result be illustrated in the table 3.
Example of the present invention is not all seen steel tube surface generation crackle, is the good steel pipe of hot workability, and the steel pipe of formation has the high strength of yield strength YS more than 413MPa.In addition, weld part crackle, excellent weldability all do not take place in example of the present invention yet, and have in the time of-60 ℃ absorb can be more than the 50J good like this welding heat affected zone toughness, and comprise mother metal portion, little in the corrosion speed of weld part, also origination point does not corrode and the sulphide stress corrosion crackle, is containing CO
2200 ℃ of harsh corrosive environments of pyritous down and under the high hydrogen sulfide environment, demonstrate sufficient corrosion resistance at welded part.
In contrast, comparative example beyond the scope of the present invention, crackle takes place in its surface, hot workability reduces, or toughness of welded zone reduces, or weld part generation crackle, or mother metal or the corrosion speed of weld part increases, the erosion resistance deterioration, or mother metal or the anti-pitting attack deterioration of weld part origination point burn into, or mother metal or weld part generation sulphide stress corrosion crackle, resistance to sulfide stress cracking deterioration.
Embodiment 2
Behind the liquid steel degassing of forming shown in the table 5, the steel ingot of casting 100kgf is as the steel pipe starting material.Use these steel pipe starting material, identical with embodiment 1, utilize the seamless milling train of model by the hot-work tubulation, make the cold or water-cooled of the laggard line space of steel pipe, make the weldless steel tube of external diameter 3.3in * wall thickness 0.5in.
To the weldless steel tube that obtains, under the state of air cooling behind the tubulation, surfaces externally and internally is investigated in range estimation flawless generation, estimates hot workability.To there be the crackle more than the length 5mm to be defined as crackle at the pipe front/rear end, in addition be defined as flawless.
In addition, to the weldless steel tube that obtains, after the heating of quenching under the conditions shown in Table 6 keeps, quench.Implement the temper shown in the table 6 again.And, the part of steel pipe is not carried out quench treatment, only carry out temper.
Identical with embodiment 1, from the weldless steel tube that obtains, take structure observation with sample, mensuration sample, calculate the tissue branch rate (volume %) of ferritic phase, the tissue branch rate (volume %) of residual austenite phase, the tissue branch rate (volume %) of martensitic phase.
And, from the weldless steel tube that obtains, take API arc tension specimen, identical with embodiment 1, implement tension test, obtain tensile properties (yield strength YS, tensile strength TS).Further from the weldless steel tube that obtains, (thickness: the absorption when 5mm), obtaining-40 ℃ can vE to take the V-notch sample
-40(J).
In addition, to the weldless steel tube that obtains, the end of similar steel pipe against each other, identical with embodiment 1, use the welding material shown in the table 4, under the welding conditions shown in the table 4, weld and make the welded tube seam.
For the welded tube seam that obtains, having or not of welding crack investigated in range estimation.
Further, take sample, implement toughness of welded zone test, weld part corrosion test, the experiment of weld part sulphide stress corrosion crackle from the welded tube seam that obtains.Experimental technique is as follows:
(1) portion's toughness experiment
On the welded tube seam that obtains,, take according to the regulation of JIS Z 2242 with the V-notch sample (thickness: 5mm), implement Charpy impact test, the absorption energy vE when asking-40 ℃ of gap position as welding heat affected zone according to the regulation of JIS Z 2202
-40(J), estimate the toughness of welding heat affected zone.
(2) weld part corrosion test
On the welded tube seam that obtains, take the corrosion sample of thick 3mm * wide 30mm * long 40mm by mechanical workout, contain welding metal, welding heat affected zone and mother metal on it.Corrosion test is identical with embodiment 1, the experimental liquid in remaining in autoclave: 20% the NaCl aqueous solution (liquid temperature: the CO under 200 ℃, 50 normal atmosphere
2In the gas atmosphere) in, the immersion corrosion sample was 2 weeks between soak period.For the sample after the corrosion test, gravimetry according to the reduction of the sample weight before and after the corrosion test, is obtained the corrosion speed of calculating.In addition, for the sample after the test, be 10 times magnifying glass with multiplying power, observe specimen surface and have or not the pitting attack generation.And, be defined as pitting attack with observing the pitting attack of diameter more than 0.2mm, be defined as no pitting attack in addition.
(3) weld part sulphide stress corrosion crack test
On the welded tube seam that obtains, by mechanical workout, that takes to stipulate in NACE-TM0177Method A decides loading type sample.The sulphide stress corrosion crack test, identical with embodiment 1, sample is remained on the experimental liquid that remains in the autoclave: the 20%NaCl aqueous solution (PH:4.0, H
2The S dividing potential drop: 0.005MPa), as 90% of mother metal yielding stress, duration of test is 72h with additional stress.To have crackle that note takes place to do *, note takes place and does zero and estimate in flawless.Gained is the result be illustrated in the table 7.
Example of the present invention is not all found out steel tube surface generation crackle, is the good steel pipe of hot workability, and the steel pipe of formation has the high strength of yield strength YS more than 413MPa, and absorb when having-40 ℃ can the above high tenacity of 50J.In addition, weld part crackle, excellent weldability all do not take place in example of the present invention, and absorb good like this welding heat affected zone toughness more than the energy 50J when having-40 ℃, and comprise mother metal portion, also little in the weld part corrosion speed, also origination point does not corrode and the sulphide stress corrosion crackle, is containing CO
2200 ℃ the harsh corrosive environment of high temperature down and under the high hydrogen sulfide environment, demonstrate sufficient erosion resistance.
In contrast, comparative example beyond scope of the present invention, crackle takes place in its surface, hot workability reduces, or the base metal tenacity reduction, or welding crack, weldability reduction take place, or toughness of welded zone reduces, or mother metal or the increase of the corrosion speed of weld part, or origination point burn into erosion resistance deterioration, or sulphide stress corrosion crackle, resistance to sulfide stress cracking deterioration take place.
The possibility of utilizing on the industry
According to the present invention, can cheap and stably make the high strength that has yield strength and surpass 413MPa (60ksi), contain CO
2, Cl
-The harsh corrosive environment of high temperature down and in the high hydrogen sulfide environment, have sufficient erosion resistance, the high strength stainless steel pipe for line pipe of low-temperature flexibility and excellent weldability proves effective on industry especially.According to the present invention, also has the effect of the welded structure of the line pipe that can constitute erosion resistance and good-toughness at an easy rate etc.
Table 1
| Grade of steel | Chemical ingredients (quality %) | (1) formula * | (2) formula * * | (3) formula * * * | Remarks | ||||||||||||||
| C | Si | Mn | P | S | Cr | Ni | Mo | V | N | O | Cu | Nb，Ti，Zr，B，W | Ca | Al | |||||
| A | 0.006 | 0.24 | 0.35 | 0.02 | 0.001 | 16.9 | 3.65 | 1.98 | 0.091 | 0.006 | 0.0029 | + | - | - | 0.001 | 20.34 | 14.85 | 0.012 | Example of the present invention |
| B | 0.005 | 0.25 | 0.36 | 0.02 | 0 001 | 17.0 | 4.06 | 1.64 | 0.075 | 0.008 | 0 0044 | 0.87 | Nb：0.046 | - | 0.001 | 21.00 | 13.96 | 0.013 | Example of the present invention |
| C | 0.009 | 0.23 | 0.37 | 0.02 | 0.001 | 16.8 | 3.49 | 2.40 | 0.046 | 0.011 | 0.0027 | 0.91 | - | 0.001 | 0.002 | 20.83 | 14.87 | 0.020 | Example of the present invention |
| D | 0.006 | 0.25 | 0.36 | 0.02 | 0.001 | 17.6 | 3.65 | 2.45 | 0.096 | 0.012 | 0.0030 | 1.28 | W：1.404 | - | 0.001 | 22.03 | 15.58 | 0.018 | Example of the present invention |
| E | 0.007 | 0.26 | 0.37 | 0.01 | 0.001 | 17.2 | 3.75 | 1.77 | 0.063 | 0.013 | 0.0026 | 0.68 | Ti：0.003，B：0.001 | - | 0.002 | 20.93 | 14.52 | 0.020 | Example of the present invention |
| F | 0.012 | 0.25 | 0.36 | 0.01 | 0.001 | 16.9 | 4.56 | 2.12 | 0.046 | 0.008 | 0.0027 | 1.17 | - | - | 0.001 | 21.54 | 13.45 | 0.020 | Example of the present invention |
| G | 0.009 | 0.24 | 0.39 | 0.02 | 0.001 | 16.8 | 4.13 | 1.86 | 0.051 | 0.006 | 0.0035 | 1.26 | Nb：0.068 | 0.002 | 0.002 | 21.11 | 13.62 | 0.015 | Example of the present invention |
| H | 0.006 | 0.22 | 0.39 | 0.01 | 0.001 | 17.5 | 3.67 | 2.30 | 0.039 | 0.008 | 0.0016 | - | Zr：0.019 | - | 0.002 | 21.15 | 15.71 | 0.014 | Example of the present invention |
| I | 0.008 | 0.25 | 0.38 | 0.01 | 0.001 | 14.7 | 3.76 | 1.63 | 0 041 | 0.008 | 0.0034 | - | - | - | 0.001 | 17.96 | 12.07 | 0.016 | Comparative example |
| J | 0.012 | 0.24 | 0.32 | 0.02 | 0.001 | 16.0 | 5.64 | 1.57 | 0.044 | 0.006 | 0.0036 | 0.58 | Ti：0.034 | - | 0.005 | 20.69 | 11.12 | 0.018 | Comparative example |
| K | 0.016 | 0.23 | 0.33 | 0.02 | 0.001 | 16.5 | 4.08 | 1.63 | 0.053 | 0.011 | 0.0030 | 0.96 | Nb：0.058 | - | 0.007 | 20.34 | 12.90 | 0.027 | Comparative example |
| L | 0.010 | 0.23 | 0.33 | 0.01 | 0.001 | 16.1 | 3.67 | 0.44 | 0.049 | 0.008 | 0.0026 | 0.85 | - | - | 0.004 | 19.04 | 12.09 | 0.018 | Comparative example |
| M | 0.008 | 0.23 | 0.39 | 0.01 | 0.001 | 16.2 | 4.19 | 2.29 | 0.062 | 0.005 | 0.0021 | - | - | - | 0.001 | 20.14 | 13.82 | 0.013 | Example of the present invention |
| N | 0.006 | 0.29 | 0.33 | 0.01 | 0.001 | 16.4 | 4.08 | 2.15 | 0.050 | 0.008 | 0.0037 | 0.75 | - | - | 0.001 | 20.63 | 13.87 | 0.014 | Example of the present invention |
| O | 0.012 | 0.26 | 0.30 | 0.02 | 0.001 | 16.5 | 4.27 | 2.34 | 0.043 | 0.011 | 0.0032 | 1.01 | T i：0.071 | - | 0.001 | 21.00 | 13.60 | 0.023 | Example of the present invention |
| P | 0.006 | 0 24 | 0.35 | 0.02 | 0.001 | 15.7 | 4.16 | 3.19 | 0.063 | 0.010 | 0.0035 | - | Nb：0.025 | 0.001 | 0.001 | 20.26 | 14.41 | 0.016 | Example of the present invention |
*) (1) formula left side value=Cr+0.65Ni+0.6Mo+0.55Cu-20C
*) (2) formula left side value=Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N
* *) (3) formula left side value=C+N
Table 2
| Steel pipe number | Grade of steel | The hot rolling postcooling | Quench treatment | Tempering | ||
| Quenching temperature ℃ | Keep temperature-time (branch) | Method of cooling | Tempering temperature ℃ | |||
| 1 | A | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 2 | B | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 3 | C | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 4 | D | Air cooling: 0.5 ℃/s | 930 | 20 | Air cooling: 0.5 ℃/s | 610 |
| 5 | E | Air cooling: 0.5 ℃/s | 870 | 20 | Water-cooled: 30 ℃/s | 610 |
| 6 | F | Air cooling: 0.5 ℃/s | 870 | 20 | Water-cooled: 30 ℃/s | 610 |
| 7 | G | Air cooling: 0.5 ℃/s | 930 | 20 | Water-cooled: 30 ℃/s | 600 |
| 8 | H | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 9 | I | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 10 | J | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 11 | K | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 610 |
| 12 | L | Air cooling; 0.5 ℃/s | 930 | 20 | Air cooling: 0.5 ℃/s | 610 |
| 13 | M | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 610 |
| 14 | N | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 610 |
| 15 | O | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 610 |
| 16 | P | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 610 |
Table 3
| Steel pipe number | Grade of steel | Hot workability | The mother metal tissue * | Strength of parent | Toughness of welded zone | Weldability | The anti-pitting attack of weld part | The weld part resistance to sulfide stress cracking | Corrosion resistance at welded part | Remarks | ||||
| Crackle has or not | Kind * | M volume % | γ volume % | F volume % | Yield strength MPa | Tensile strength MPa | vE -60 (J) | Welding crack has or not | Having or not of pitting attack | Having or not of thinization thing stress corrosion cracking | Corrosion speed (mm/yr) | |||
| 1 | A | ○ | M+γ+F | 54.7 | 5.5 | 39.8 | 568 | 672 | 92 | ○ | ○ | ○ | 0.10 | Example of the present invention |
| 2 | B | ○ | M+γ+F | 54.7 | 12.8 | 32.5 | 524 | 689 | 95 | ○ | ○ | ○ | 0.09 | Example of the present invention |
| 3 | C | ○ | M+γ+F | 45.3 | 13.4 | 41.3 | 491 | 674 | 108 | ○ | ○ | ○ | 0.09 | Example of the present invention |
| 4 | D | ○ | M+γ+F | 33.3 | 21.6 | 45.1 | 512 | 671 | 160 | ○ | ○ | ○ | 0.07 | Example of the present invention |
| 5 | E | ○ | M+γ+F | 48.3 | 12.6 | 39.1 | 535 | 657 | 97 | ○ | ○ | ○ | 0.09 | Example of the present invention |
| 6 | F | ○ | M+γ+F | 29.4 | 36.5 | 34.1 | 476 | 615 | 188 | ○ | ○ | ○ | 0.08 | Example of the present invention |
| 7 | G | ○ | M+γ+F | 50.2 | 19.4 | 30.4 | 537 | 663 | 152 | ○ | ○ | ○ | 0.08 | Example of the present invention |
| 8 | H | ○ | M+γ+F | 29.9 | 11.4 | 58.7 | 538 | 631 | 91 | ○ | ○ | ○ | 0.09 | Example of the present invention |
| 9 | I | ○ | M+γ+F | 87.6 | 7.2 | 5.2 | 591 | 697 | 68 | ○ | × | × | 0.29 | Comparative example |
| 10 | J | × | M+γ+F | 78.4 | 15.3 | 6.3 | 569 | 675 | 49 | ○ | × | ○ | 0.10 | Comparative example |
| 11 | K | ○ | M+γ+F | 71.6 | 11.7 | 16.7 | 579 | 677 | 48 | × | × | ○ | 0.10 | Comparative example |
| 12 | L | ○ | M+γ+F | 79.8 | 7.5 | 12.7 | 557 | 671 | 46 | ○ | × | × | 0.11 | Comparative example |
| 13 | M | ○ | M+γ+F | 48.8 | 16.5 | 39.7 | 527 | 651 | 123 | ○ | ○ | ○ | 0.07 | Example of the present invention |
| 14 | N | ○ | M+γ+F | 48.1 | 17.1 | 34.8 | 531 | 656 | 117 | ○ | ○ | ○ | 0.06 | Example of the present invention |
| 15 | O | ○ | M+γ+F | 48.6 | 18.4 | 33.0 | 538 | 622 | 125 | ○ | ○ | ○ | 0.05 | Example of the present invention |
| 16 | P | ○ | M+γ+F | 46.5 | 16.8 | 36.7 | 515 | 649 | 93 | ○ | ○ | ○ | 0.07 | Example of the present invention |
*) M: martensite, γ: residual austenite, F: ferrite
Table 4
| Welding process | Welding material chemical ingredients (quality %) | Shielding gas | Heating | ||||||||
| C | Si | Mn | P | S | Cr | Ni | Mo | N | |||
| GMAW | 0.012 | 0.33 | 0.46 | 0.02 | 0.001 | 24.6 | 9.7 | 1.55 | 0.011 | 98％Ar+ 2％CO 2 | 1.0～1.5Kj/mm |
Table 5
| Grade of steel | Chemical ingredients (quality %) | (1) formula * | (2) formula * * | (3) formula * * * | ||||||||||||||
| C | Si | Mn | P | S | Al | Cr | Ni | Mo | V | N | O | Cu | Nb，Ti，Zr，B，W | Ca | ||||
| 2A | 0.005 | 0.25 | 0.31 | 0.02 | 0.001 | 0.01 | 17.2 | 3.06 | 1.30 | 0.055 | 0.008 | 0.0036 | - | - | - | 19.87 | 15.1 | 0.013 |
| 2B | 0.012 | 0.25 | 0.40 | 0.01 | 0.001 | 0.01 | 16.6 | 3.11 | 1.64 | 0.085 | 0.006 | 0 0038 | 1.13 | Nb：0.049 | - | 19.99 | 14.1 | 0.018 |
| 2C | 0.011 | 0.23 | 0.37 | 0.01 | 0.001 | 0.01 | 15.9 | 3.58 | 2.27 | 0.092 | 0.004 | 0.0035 | 1.41 | - | 0.003 | 20.14 | 13.6 | 0.015 |
| 2D | 0.009 | 0.25 | 0.37 | 0.02 | 0.001 | 0.01 | 17.6 | 4.14 | 1.67 | 0.088 | 0.008 | 0.0037 | 0.64 | W：1.14 | - | 21.47 | 14.4 | 0.017 |
| 2E | 0.006 | 0.25 | 0.30 | 0.01 | 0.001 | 0.01 | 17.0 | 3.97 | 1.73 | 0.014 | 0.012 | 0.0038 | 0.78 | Ti：0.027，B：0.001 | - | 20.93 | 14.1 | 0.018 |
| 2F | 0.006 | 0.25 | 0.35 | 0.01 | 0.001 | 0.01 | 17.1 | 3.92 | 1.97 | 0.055 | 0.006 | 0.0043 | 1.71 | - | - | 21.65 | 14.3 | 0.012 |
| 2G | 0.007 | 0.22 | 0.31 | 0.01 | 0.001 | 0.01 | 17.7 | 3.66 | 2.50 | 0.027 | 0.007 | 0.0027 | 1.62 | Nb：0.058 | 0.002 | 22.33 | 15.6 | 0.014 |
| 2H | 0.010 | 0.22 | 0.37 | 0.02 | 0.001 | 0.01 | 16.9 | 4.25 | 1.96 | 0.036 | 0.009 | 0.0036 | - | Zr：0.001 | - | 20.64 | 14.0 | 0.019 |
| 2I | 0.012 | 0.26 | 0.35 | 0.01 | 0.001 | 0.01 | 14.8 | 3.22 | 1.92 | 0.073 | 0.012 | 0.0038 | - | - | - | 17.81 | 12.8 | 0.024 |
| 2J | 0.009 | 0.29 | 0.31 | 0.01 | 0.002 | 0.02 | 16.1 | 5.32 | 1.42 | 0.051 | 0.010 | 0.0030 | 0.69 | Ti：0.024 | - | 20.61 | 11.5 | 0.019 |
| 2K | 0.016 | 0.27 | 0.34 | 0.02 | 0.001 | 0.02 | 16.2 | 3.63 | 1.48 | 0.067 | 0.012 | 0.0028 | 1.12 | Nb：0.047 | - | 19.74 | 12.9 | 0.028 |
| 2L | 0.011 | 0.25 | 0.39 | 0.02 | 0.001 | 0.01 | 16.9 | 3.27 | 0.44 | 0.019 | 0.011 | 0.0029 | 1.01 | - | - | 19.63 | 13.1 | 0.022 |
| 2 | 0.012 | 0.25 | 0.33 | 0 02 | 0.001 | 0.01 | 16.0 | 4.23 | 2.41 | 0.055 | 0.011 | 0.0032 | - | - | - | 19.96 | 13.5 | 0.023 |
| 2N | 0.008 | 0.22 | 0.35 | 0.01 | 0.001 | 0.01 | 16.4 | 4.09 | 2.36 | 0.062 | 0.009 | 0.0036 | 0.95 | Ti：0.064 | - | 20.84 | 13.9 | 0.017 |
| 2O | 0.011 | 0.25 | 0.34 | 0.02 | 0.001 | 0.01 | 15.7 | 3.78 | 2.74 | 0.059 | 0.007 | 0.0024 | 1.12 | Nb：0.051 | - | 20.20 | 13.7 | 0.018 |
| 2P | 0.006 | 0.29 | 0.33 | 0.02 | 0.001 | 0.01 | 16.3 | 4.28 | 2.25 | 0.055 | 0.009 | 0.0028 | - | - | - | 20.31 | 13.9 | 0.015 |
*) (1) formula left side value=Cr+0.65Ni+0.6Mo+0.55Cu-20C
*) (2) formula left side value=Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N
* *) (3) formula left side value=C+N
Table 6
| Steel pipe number | Grade of steel | The hot rolling postcooling | Quench treatment | Tempering | ||
| Quenching temperature ℃ | Hold-time min | Speed of cooling *℃/s | Tempering temperature ℃ | |||
| 21 | 2A | Air cooling: 0.5 ℃/s * | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 22 | 2B | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 23 | 2C | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 24 | 2D | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 25 | 2E | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 26 | 2F | Air cooling: 05 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 27 | 2G | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 28 | 2H | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 29 | 2I | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 30 | 2J | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 31 | 2K | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 32 | 2L | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 33 | 2A | Air cooling: 0.5 ℃/s | 900 | 30 | Air cooling: 0.5 ℃/s | 600 |
| 34 | 2B | Air cooling: 0.5 ℃/s | 930 | 30 | Air cooling: 0.5 ℃/s | 600 |
| 35 | 2B | Air cooling: 0.5 ℃/s | - | - | - | 600 |
| 36 | 2M | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 37 | 2N | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 38 | 2O | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
| 39 | 2P | Air cooling: 0.5 ℃/s | 890 | 20 | Air cooling: 0.5 ℃/s | 600 |
*Average cooling rate between 800～500 ℃
Table 7
| Steel pipe number | Grade of steel | The mother metal tissue | Hot workability | Strength of parent | Base metal tenacity | Weldability | Toughness of welded zone | The weld part resistance to sulfide stress cracking | Corrosion resistance at welded part | Remarks | |||||
| Kind * | Martensite volume % | Austenite volume % | Ferrite volume % | Crackle has or not | Yield strength MPa | Tensile strength MPa | VE _40 J | Welding crack has or not | VE _40 J | Having or not of sulphide stress corrosion crackle | Corrosion speed mm/yr | Having or not of pitting attack | |||
| 21 | 2A | M，γ，F | 32.4 | 6.2 | 61.4 | ○ | 492 | 620 | 153 | ○ | 107 | ○ | 0 10 | ○ | Example of the present invention |
| 22 | 2B | M，γ，F | 39.2 | 19.9 | 40.9 | ○ | 497 | 640 | 169 | ○ | 121 | ○ | 0.10 | ○ | Example of the present invention |
| 23 | 2C | M，γ，F | 29.4 | 36.9 | 33.7 | ○ | 479 | 669 | 192 | ○ | 135 | ○ | 0 09 | ○ | Example of the present invention |
| 24 | 2D | M，γ，F | 42.3 | 14.1 | 43.6 | ○ | 529 | 598 | 184 | ○ | 147 | ○ | 0.06 | ○ | Example of the present invention |
| 25 | 2E | M，γ，F | 54.5 | 4.9 | 40.6 | ○ | 569 | 624 | 194 | ○ | 161 | ○ | 0.09 | ○ | Example of the present invention |
| 26 | 2F | M，γ，F | 31.5 | 27.1 | 41.4 | ○ | 483 | 625 | 232 | ○ | 137 | ○ | 0.06 | ○ | Example of the present invention |
| 27 | 2G | M，γ，F | 28.6 | 4.1 | 67.3 | ○ | 534 | 644 | 173 | ○ | 118 | ○ | 0.05 | ○ | Example of the present invention |
| 28 | 2H | M，γ，F | 52.3 | 15.3 | 37.4 | ○ | 520 | 652 | 226 | ○ | 179 | ○ | 0.08 | ○ | Example of the present invention |
| 29 | 2I | M，γ，F | 59.8 | 23.8 | 16.4 | ○ | 493 | 612 | 179 | ○ | 135 | × | 0.31 | ○ | Comparative example |
| 30 | 2J | M，γ，F | 58.5 | 36.8 | 4.7 | × | 467 | 591 | 194 | ○ | 163 | ○ | 0.09 | ○ | Comparative example |
| 31 | 2K | M，γ，F | 65.2 | 16.6 | 18.2 | ○ | 531 | 638 | 88 | × | 52 | ○ | 0.10 | ○ | Comparative example |
| 32 | 2L | M，γ，F | 60.9 | 12.4 | 26.7 | ○ | 522 | 641 | 172 | ○ | 102 | × | 0.11 | × | Comparative example |
| 33 | 2A | M，γ，F | 33.8 | 5.7 | 60.5 | - | 501 | 634 | 177 | ○ | 111 | ○ | 0.10 | ○ | Example of the present invention |
| 34 | 2B | M，γ，F | 42.6 | 18.0 | 39.4 | - | 535 | 637 | 187 | ○ | 126 | ○ | 0.10 | ○ | Example of the present invention |
| 35 | 2B | M，γ，F | 52.3 | 7.6 | 40.1 | ○ | 573 | 674 | 178 | ○ | 109 | ○ | 0.10 | ○ | Example of the present invention |
| 36 | 2M | M，γ，F | 47.6 | 18.6 | 33.8 | ○ | 564 | 679 | 164 | ○ | 129 | ○ | 0.08 | ○ | Example of the present invention |
| 37 | 2N | M，γ，F | 46.9 | 20.4 | 32.7 | ○ | 560 | 674 | 159 | ○ | 112 | ○ | 0.07 | ○ | Example of the present invention |
| 38 | 2O | M，γ，F | 48.2 | 18.2 | 33.6 | ○ | 579 | 684 | 160 | ○ | 131 | ○ | 0.08 | ○ | Example of the present invention |
| 39 | 2P | M，γ，F | 48.6 | 18.5 | 32.9 | ○ | 561 | 666 | 155 | ○ | 123 | ○ | 0.08 | ○ | Example of the present invention |
*) M: martensite, F: ferrite, γ: residual austenite
Claims (24)
1. the high strength stainless steel pipe for line pipe of excellent corrosion resistance is characterized in that, it has
% contains in quality
C：0.001～0.015％ Si：0.01～0.5％
Mn:0.1～below 1.8% P:0.03%
The following Cr:15 of S:0.005%～18%
Above and less than 5.5% Mo:0.5～3.5% of Ni:0.5%
V：0.02～0.2％ N：0.001～0.015％
Below the O:0.006%
So that satisfy following (1), (2) and (3) formula, surplus is Fe and unavoidable impurities
Composition,
Cr+0.65Ni+0.6Mo+0.55Cu-20C≥18.5 …(1)
Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5…(2)
C+N≤0.025 …(3)
Wherein, C, Ni, Mo, Cr, Si, Mn, Cu, N represent the content (quality %) of each element.
2. high strength stainless steel pipe for line pipe as claimed in claim 1 is characterized in that, except that above-mentioned composition, also has the composition that contains Al:0.002～0.05% in quality %.
3. high strength stainless steel pipe for line pipe as claimed in claim 1 or 2 is characterized in that, in quality %, the content of described Ni is 1.5～5.0%.
4. as each described high strength stainless steel pipe for line pipe in the claim 1～3, it is characterized in that in quality %, the content of described Mo is 1.0～3.5%.
5. as each described high strength stainless steel pipe for line pipe in the claim 1～3, it is characterized in that in quality %, the content of described Mo is greater than 2% and is no more than 3.5%.
6. as each described high strength stainless steel pipe for line pipe in the claim 1～5, it is characterized in that except that above-mentioned composition, also having in quality % and contain composition below the Cu:3.5%.
7. high strength stainless steel pipe for line pipe as claimed in claim 6 is characterized in that, in quality %, the content of described Cu is 0.5%～1.14%.
8. as each described high strength stainless steel pipe for line pipe in the claim 1～7, it is characterized in that, except that above-mentioned composition, also have in quality % and contain the composition more than a kind or 2 kinds that is selected from below the Nb:0.2%, below the Ti:0.3%, below the Zr:0.2%, below the B:0.01% and in below the W:3.0%.
9. as each described high strength stainless steel pipe for line pipe in the claim 1～8, it is characterized in that except that above-mentioned composition, also having in quality % and contain composition below the Ca:0.01%.
10. as each described high strength stainless steel pipe for line pipe in the claim 1～9, it is characterized in that, except that above-mentioned composition, also have with martensitic phase as basic phase, in volume ratio contain below 40% retained austenite mutually and the tissue of 10～60% ferritic phase.
11. high strength stainless steel pipe for line pipe as claimed in claim 10 is characterized in that, described ferritic phase counts 15～50% with volume ratio.
12., it is characterized in that described retained austenite is counted below 30% with volume ratio as claim 10 or 11 described high strength stainless steel pipe for line pipe.
13. the manufacture method of the high strength stainless steel pipe for line pipe of excellent corrosion resistance is characterized in that, will have
Contain
C：0.001～0.015％ Si：0.01～0.5％
Mn:0.1～below 1.8% P:0.03%
The following Cr:15 of S:0.005%～18%
Above and less than 5.5% Mo:0.5～3.5% of Ni:0.5%
V：0.02～0.2％ N：0.001～0.015％
Below the O:0.006%
So that satisfy following (1), (2) and (3) formula, surplus is Fe and unavoidable impurities
The steel pipe starting material of composition, make the steel pipe of specified dimension, with the temperature more than this steel pipe reheat to 850 ℃, be cooled to below 100 ℃ with the above speed of cooling of air cooling speed then, then, implement to be heated to the quenching-temper of the temperature below 700 ℃
Cr+0.65Ni+0.6Mo+0.55Cu-20C≥18.5 …(1)
Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5…(2)
C+N≤0.025 …(3)
Wherein, Cr, Ni, Mo, Cu, C, Si, Mn, N represent the content (quality %) of each element.
14. the manufacture method of high strength stainless steel pipe for line pipe as claimed in claim 13, it is characterized in that, described steel pipe starting material are heated, by the hot-work tubulation, behind the tubulation, be cooled to room temperature with the speed of cooling more than the air cooling speed, make the weldless steel tube of specified dimension, then this weldless steel tube is implemented described quenching-temper.
15. the manufacture method as claim 13 or 14 described high strength stainless steel pipe for line pipe is characterized in that, replaces described quenching-temper, implements to be heated to the temper of the temperature below 700 ℃.
16. the manufacture method as each described high strength stainless steel pipe for line pipe in the claim 13～15 is characterized in that, removes above-mentioned composition part, has the composition that contains Al:0.002～0.05% in quality %.
17. the manufacture method as each described high strength stainless steel pipe for line pipe in the claim 13～16 is characterized in that, in quality %, the content of described Ni is 1.5～5.0%.
18. the manufacture method as each described high strength stainless steel pipe for line pipe in the claim 13～17 is characterized in that, in quality %, the content of described Mo is 1.0～3.5%.
19. the manufacture method as each described high strength stainless steel pipe for line pipe in the claim 13～17 is characterized in that, in quality %, the content of described Mo is greater than 2% and is no more than 3.5%.
20. the manufacture method as each described high strength stainless steel pipe for line pipe in the claim 13～19 is characterized in that, except that above-mentioned composition, % also contains below the Cu:3.5% in quality.
21. the manufacture method of high strength stainless steel pipe for line pipe as claimed in claim 20 is characterized in that, in quality %, the content of described Cu is 0.5%～1.14%.
22. manufacture method as each described high strength stainless steel pipe for line pipe in the claim 13～21, it is characterized in that, except that above-mentioned composition, also contain in quality % be selected from below the Nb:0.2%, below the Ti:0.3%, below the Zr:0.2%, below the W:3% and in below the B:0.01% more than a kind or 2 kinds.
23. the manufacture method as each described high strength stainless steel pipe for line pipe in the claim 13～22 is characterized in that, except that above-mentioned composition, % also contains below the Ca:0.01% in quality.
24. the welding structure thing, it is by forming each described high strength stainless steel pipe welded joint in the claim 1～12.
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| JP373404/2003 | 2003-10-31 | ||
| JP2003373404 | 2003-10-31 | ||
| JP038854/2004 | 2004-02-16 | ||
| JP117445/2004 | 2004-04-13 | ||
| JP135973/2004 | 2004-04-30 |
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