CN100451153C - High strength stainless steel pipe excellent in corrosion resistance for use in oil well and method for production thereof - Google Patents
High strength stainless steel pipe excellent in corrosion resistance for use in oil well and method for production thereof Download PDFInfo
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- CN100451153C CN100451153C CNB2004800235571A CN200480023557A CN100451153C CN 100451153 C CN100451153 C CN 100451153C CN B2004800235571 A CNB2004800235571 A CN B2004800235571A CN 200480023557 A CN200480023557 A CN 200480023557A CN 100451153 C CN100451153 C CN 100451153C
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Abstract
A stainless steel pipe for use in oil wells is proposed which has a high strength having a YS of 654 MPa or more and superior corrosion resistance even in a severe corrosive environment in which CO 2 and Cl - are present and the temperature is high, such as up to 230 DEG C. As specific solution means, a pipe contains on a mass percent basis: 0.005% to 0.05% of C; 0.05% to 0.5% of Si; 0.2% to 1.8% of Mn; 0.03% or less of P; 0.005% or less of S; 15.5% to 18% of Cr; 1.5% to 5% of Ni; 1% to 3.5% of Mo; 0.02% to 0.2% of V; 0.01% to 0.15% of N; 0.006% or less of O; and the balance being Fe and unavoidable impurities, in which Cr+0.65Ni+0.6Mo+0.55Cu-20C 19.5 and Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N 11.5 are satisfied (where Cr, Ni, Mo, Cu, C, Si, Mn, and N represent the respective contents on a mass percent basis). In addition, quenching treatment and tempering treatment are preferably performed, so that the pipe preferably has a texture containing a martensite phase as a primary phase and 10 to 60 percent by volume of a ferrite phase, or further containing 30 percent by volume or less of an austenite phase. Furthermore, at least one of Al, Cu, Nb, Ti, Zr, W, B, and Ca may also be contained.
Description
Technical field
The present invention relates to the employed oil well steel pipe of oil well, gas well of a kind of crude oil or Sweet natural gas.Be particularly related to a kind of carbon dioxide (CO that is fit to contain
2), chlorion (Cl
-) wait very oil well, the gas well oil well high strength stainless steel pipe that use, that have superior corrosion resistance of heavy corrosion environment.In addition, so-called in the present invention " high strength stainless steel pipe " is meant to have the stainless steel tube of yield strength in the above intensity of 654MPa (95ksi).
Background technology
In recent years, exhaustion for the rise of tackling crude oil price and the petroleum resources envisioned in the near future, for never planned the exploitation of the stronger sulfide hydrogen natural-gas field of corrodibility that the deep layer oil field and once abandoning of exploitation develops etc. in the past, worldwide prevail.Such gas field, oil field generally is very dark, and its atmosphere also is the condition of high temperature, and contains CO
2, Cl
-Deng serious corrosive environment.Thereby such oil field, the employed oil well steel pipe of gas-field exploitation require its steel pipe to have higher intensity and have superior corrosion resistance.
In the past, containing CO
2, Cl
-In the oil field under the environment, gas field,, generally use anti-CO as the oil well steel pipe
2The 13%Cr martensite stainless steel pipe that corrodibility is good., common martensitic stainless steel is containing Cl in a large number
-And surpass under 100 ℃ the hot environment, short-life problem is arranged.Therefore, in requiring corrosion resistant well, use the two phase stainless steel pipe., two phase stainless steel pipe alloying element amount is more, and hot workability is relatively poor, can only have the high problem of its cost value with special thermal processing method manufacturing.And, 13%Cr martensite stainless steel pipe in the past, when its yield strength surpassed 654MPa, the toughness of steel pipe obviously reduced, and short-life problem is also arranged.
In addition, in recent years, also enliven in the oil-field development of cold district, majority requires its steel pipe to have high strength and good low-temperature flexibility.
From above-mentioned situation, more wish to have following oil well high strength 13%Cr martensite stainless steel pipe, it, has the high strength that yield strength surpasses 654MPa (95ksi), and has good anti-CO as substrate with good, the cheap 13%Cr martensitic stainless steel of hot workability
2Corrodibility and high tenacity.
For such requirement, for example in patent documentation 1, patent documentation 2, patent documentation 3, patent documentation 4, patent documentation 5, proposed to improve the modified form martensitic stainless steel or the steel pipe of the erosion resistance of 13%Cr martensitic stainless steel or steel pipe.
The technology of patent documentation 1 record is a kind of manufacture method with martensitic stainless steel weldless steel tube of superior corrosion resistance.To C being limited in more than 0.005%, below 0.05%, more than the compound interpolation Ni:2.4%, below 6%, more than the Cu:0.2%, below 4%, add again more than the Mo:0.5%, below 3%, further Nieq is adjusted into the 13%Cr martensite stainless steel pipe starting material of the composition more than 10.5, after after hot-work, cooling off, be heated to (Ac with the speed more than the air cooling
3Transformation temperature+10 ℃) above, (Ac
3Transformation temperature+200 ℃) following temperature, perhaps reheat is to Ac
1Transformation temperature is above, Ac
3The temperature that transformation temperature is following then with the speed of cooling cool to room temperature more than the air cooling, is carried out tempering.According to the technology of being put down in writing in the patent documentation 1, can make and have the above high strength of API-C95 level concurrently, at the CO that contains more than 180 ℃
2Environment under erosion resistance and the martensitic stainless steel weldless steel tube of SCC resistance.
The technology of patent documentation 2 records is a kind of manufacture method with the good martensitic stainless steel weldless steel tube of the crackle of anti-sulphide stress corrosion property.To contain more than the C:0.005%, below 0.05%, more than the N:0.005%, below 0.1%, be adjusted into more than the Ni:3.0%, below 6.0%, more than the Cu:0.5%, below 3%, Mo:0.5% is above, the 13%Cr martensitic stainless steel of the composition below 3% carries out hot-work, naturally place after the cool to room temperature, be heated to (Ac
1Point+10 ℃) above, (Ac
1Point+40 ℃) following temperature kept 30 minutes to 60 minutes, was cooled to the following temperature of Ms point, at Ac
1Carry out tempering under the following temperature of point, tissue is carried out tempering, form the tissue that martensite and the above γ of 20 volume % mix existence mutually.According to the technology of patent documentation 2 record, contain the tempered martensite of the γ phase more than the 20 volume % by formation, the crackle of anti-sulphide stress corrosion property be improved significantly.
The technology of being put down in writing in patent documentation 3 is the good martensitic stainless steel of erosion resistance, the crackle of anti-sulphide stress corrosion property.Its composition be contain more than 10%, the composition of the martensitic stainless steel of 15% following Cr, C is more than 0.005%, below 0.05% in restriction, more than the compound interpolation Ni:4.0%, more than the Cu:0.5%, below 3%, add Mo again more than 1.0%, below 3.0%, further adjust Nieq to more than-10, its tissue is made of mutually tempered martensite phase, martensitic phase, residual austenite, and wherein the percent of total of tempered martensite phase, martensitic phase is more than 60%, below 90%.Thus, make under the moistening carbon dioxide environment and erosion resistance and the raising of the crackle of anti-sulphide stress corrosion property under the moistening hydrogen-sulfide environmental.
The technology of being put down in writing in patent documentation 4 is the oil well martensitic stainless steel material with good SSC, this steel consists of: contain Cr: surpass 15%, below 19%, below the C:0.05%, below the N:0.1%, more than the Ni:3.5%, below 8.0%, and then contain Mo:0.1% above, below 4.0%, satisfy 30Cr+36Mo+14Si-28Ni≤455 (%), 21Cr+25Mo+17Si+35Ni≤731 (%) simultaneously.Even obtain in the harsh oil well environment that chloride ion, carbonic acid gas and micro-hydrogen sulfide exist the steel that also have superior corrosion resistance thus.
The technology of being put down in writing in patent documentation 5 is a kind ofly to have good intensity and flexible is separated out the curing martensitic stainless steel.It is more than 10.0%, below 17% that its steel composition contains Cr, and contain below the C:0.08%, below the N:0.015%, more than the Ni:6.0%, below 10.0%, more than the Cu:0.5%, below 2.0%, and contain more than the Mo:0.5%, below 3.0%, it is by cold working and annealing more than 35%, obtain having the average crystallite particle diameter below 25 μ m, separate out the particle diameter 5 * 10 on matrix
-2The above precipitate of μ m is suppressed at 6 * 10
6Individual/mm
2Following tissue.The technology of being put down in writing according to patent documentation 5, by forming the few tissue of fine crystal grain and precipitate, can provide high-intensity can not cause that toughness reduces separate out the curing martensitic stainless steel.
Patent documentation 1: the spy opens flat 8-120345 communique
Patent documentation 2: the spy opens flat 9-268349 communique
Patent documentation 3: the spy opens flat 10-1755 communique
Patent documentation 4: specially permit communique No. 2814528
Patent documentation 5: specially permit communique No. 3251684
Summary of the invention
Yet modified form 13% martensite stainless steel pipe with the technology of being put down in writing in patent documentation 1, patent documentation 2, patent documentation 3, patent documentation 4, the patent documentation 5 is made is containing CO
2, Cl
-Deng, surpassing under the harsh corrosive environment of 180 ℃ of pyritous, existence can not stably show the problem of the erosion resistance of expectation.
The present invention is based on that present technical situation finishes.The object of the present invention is to provide a kind of oil well high strength stainless steel pipe and manufacture method thereof with superior corrosion resistance.This steel pipe cheapness, have good hot workability, have the high strength that yield strength surpasses 654MPa, and, even containing CO
2, Cl
-Under 230 ℃ of harsh corrosive environments of pyritous, also can demonstrate good anti-CO
2Corrodibility.
The present inventor has carried out wholwe-hearted research for finishing above-mentioned problem to the various factors that relates to hot workability, erosion resistance.
Aspect present 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.So, put down in writing as opening the spy in the flat 8-246107 communique, generally speaking, can be adjusted into and suppress ferritic generation so that be organized as the monophasic composition of martensite, make oil well 13%Cr class martensitic stainless steel weldless steel tube.
Therefore, the present inventor has further carried out detailed research to the influence of the composition that relates to hot workability.It found that: make it satisfy following formula (2) 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-0.4Mn-Ni-0.3Cu-9N≥11.5 ………(2)
(wherein, Cr, Ni, Mo, Cu, C, Si, Mn, N are the content (quality %) of each element)
(2) when the value on the formula left side and hot-work the relation of (, when making weldless steel tube) crack length of taking place at the end face of 13%Cr class stainless-steel seamless pipe as shown in Figure 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 the value change on (2) formula left side is 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 length of the crackle that takes place at the end face of 13%Cr class stainless-steel seamless pipe is put in order with the relation of itself and ferrite content, is illustrated among Fig. 2.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, and is generating the ferritic crackle that takes place simultaneously., further increase the ferritic amount of generation, make its volume fraction more than 10%, different when preferably generating the ferritic phase more than 15% with present viewpoint, can prevent crackle.That is, adjust its composition to satisfy formula (2), make its ferritic phase that generates proper range, form ferrite-martensitic two phase constitutions, its hot workability improves thus, can prevent crackle.And,, also can guarantee the needed intensity of oil well pipe by forming ferrite-martensitic two phase constitutions.
, adjust its composition and satisfy formula (2), when its tissue becomes ferrite-martensitic two phase constitutions, 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, compare with uniform tissue, probably its erosion resistance reduces.
So the present inventor has carried out wholwe-hearted research to the influence of the composition that relates to erosion resistance.It found that: by adjusting its composition to satisfy following formula (1), even its tissue becomes ferrite-martensitic two phase constitutions, also can guarantee its sufficient erosion resistance.
Cr+0.65Ni+0.6Mo+0.55Cu-20C≥19.5 …(1)
(wherein, Cr, Ni, Mo, Cu, C are the content (quality %) of each element)
The value on formula (1) left side and contain CO
2And Cl
-230 ℃ hot environment under corrosion speed relation as shown in Figure 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
-230 ℃ 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 make it to contain amount with the matched Ni element of Cr content in the past for reaching., when the amount that adapts to the Cr element increased the amount of Ni element, austenite was with regard to stabilization, and existence can not be guaranteed the problem of the needed intensity of oil well pipe.
For this problem, the present inventor finds, by under the state of the ferrite of keeping the ferritic phase that contains appropriate amount-martensitic two phase constitutions, increasing Cr content, can hang down the residual quantity that suppresses the austenite phase, can guarantee full intensity as oil well 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 table 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.By Fig. 4 latest find, by tissue being maintained comprise ferrite-martensite two phase constitutions of the ferritic phase of appropriate amount, increase the content of Cr, can guarantee the oil well pipe full intensity.On the other hand, make when being organized as single-phase or martensite-austenite two phase constitutions of martensite, when increasing Cr content, YS reduces.
The present invention is based on above-mentioned opinion and has carried out wholwe-hearted research and finished.That is, main points of the present invention are as follows:
(1) a kind of oil well high strength stainless steel pipe of excellent corrosion resistance is characterized in that, its composition contains in quality %:
More than the C:0.005%, below 0.05%, more than the Si:0.05%, below 0.5%, more than the Mn:0.2%, below 1.8%, below the P:0.03, below the S:0.005%, more than the Cr:15.5%, below 18%, more than the Ni:1.5%, below 5%, more than the Mo:1%, below 3.5%, more than the V:0.02%, below 0.2%, more than the N:0.01%, below 0.15%, below the O:0.006%, and satisfy following formula (1) and formula (2), surplus is made of Fe and unavoidable impurities
Cr+0.65Ni+0.6Mo+0.55Cu-20C≥19.5 …(1)
Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 …(2)
Wherein, Cr, Ni, Mo, Cu, C, Si, Mn, N are the content (quality %) of each element.
(2) as (1) described oil well high strength stainless steel pipe, it is characterized in that having outside described composition in quality % and also contain composition more than the Al:0.002%, below 0.05%.
As (1) or (2) described oil well high strength stainless steel pipe, it is characterized in that (3) in quality %, the content of described C is more than 0.03%, below 0.05%.
(4) as each described oil well high strength stainless steel pipe in (1)～(3), it is characterized in that, the content of described Cr more than 16.6%, less than 18%.
As each described oil well high strength stainless steel pipe in (1)～(4), it is characterized in that (5) in quality %, the content of described Mo is more than 2%, below 3.5%.
(6) as each described oil well high strength stainless steel pipe in (1)～(5), it is characterized in that having outside described composition in quality % and also contain composition below the Cu:3.5%.
As (6) described oil well high strength stainless steel pipe, it is characterized in that (7) in quality %, the content of described Cu is more than 0.5%, below 1.14%.
(8) as each described oil well high strength stainless steel pipe in (1)～(7), it is characterized in that, have outside described composition, also contain in quality % and to be selected from below the Nb:0.2%, below the Ti:0.3%, below the Zr:0.2%, below the W:3%, the composition more than a kind or 2 kinds during B:0.01% is following.
(9) as each described oil well high strength stainless steel pipe in (1)～(8), it is characterized in that having outside described composition in quality % and also contain composition below the Ca:0.01%.
(10) as each described oil well high strength stainless steel pipe in (1)～(9), it is characterized in that having with martensitic phase, also contain the tissue that volume fraction is the ferritic phase more than 10%, below 60% as basic phase.
As (10) described oil well high strength stainless steel pipe, it is characterized in that (11) volume fraction of described ferritic phase is more than 15%, below 50%.
(12) as (10) or (11) described oil well high strength stainless steel pipe, it is characterized in that, describedly organize that also to contain volume fraction be austenite phase below 30%.
(13) a kind of oil well of excellent corrosion resistance manufacture method of high strength stainless steel pipe, it is characterized in that, to have in quality % and contain more than the C:0.005%, below 0.05%, more than the Si:0.05%, below 0.5%, more than the Mn:0.2%, below 1.8%, below the P:0.03, below the S:0.005%, more than the Cr:15.5%, below 18%, more than the Ni:1.5%, below 5%, more than the Mo:1%, below 3.5%, more than the V:0.02%, below 0.2%, more than the N:0.01%, below 0.15%, below the O:0.006%, and satisfy following formula (1) and formula (2), the steel pipe starting material of forming that surplus is made of Fe and unavoidable impurities, make the steel pipe of specified dimension, after the temperature more than this steel pipe reheat to 850 ℃, the speed of cooling above with air cooling is cooled to below 100 ℃, then, enforcement is heated to the quenching-temper of the temperature below 700 ℃
Cr+0.65Ni+0.6Mo+0.55Cu-20C≥19.5 …(1)
Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 …(2)
Wherein, Cr, Ni, Mo, Cu, C, Si, Mn, N are the content (quality %) of each element.
(14) as the manufacture method of (13) described oil well with high strength stainless steel pipe, it is characterized in that, described steel pipe starting material are heated, make pipe by hot-work, after making pipe, be cooled to room temperature with the speed of cooling more than the air cooling, 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 oil well, it is characterized in that, replace described quenching-temper, implement to be heated to the temper of the temperature below 700 ℃ with high strength stainless steel pipe.
(16) it is characterized in that having outside described composition in quality % and also contain composition more than the Al:0.002%, below 0.05% with the manufacture method of high strength stainless steel pipe as each described oil well in (13)～(15).
(17) it is characterized in that with the manufacture method of high strength stainless steel pipe in quality %, the content of described C is more than 0.03%, below 0.05% as each described oil well in (13)～(16).
(18) it is characterized in that with the manufacture method of high strength stainless steel pipe as each described oil well in (13)～(17), the content of described Cr more than 16.6%, less than 18%.
(19) it is characterized in that with the manufacture method of high strength stainless steel pipe in quality %, the content of described Mo is more than 2%, below 3.5% as each described oil well in (13)～(18).
(20) it is characterized in that having outside described composition in quality % and also contain composition below the Cu:3.5% with the manufacture method of high strength stainless steel pipe as each described oil well in (13)～(19).
(21) as the manufacture method of (20) described oil well, it is characterized in that in quality %, the content of described Cu is more than 0.5%, below 1.14% with high strength stainless steel pipe.
(22) as each described oil well in (13)～(21) with the manufacture method of high strength stainless steel pipe, it is characterized in that, have outside described composition, also contain in quality % and to be selected from below the Nb:0.2%, below the Ti:0.3%, below the Zr:0.2%, below the W:3%, the composition more than a kind or 2 kinds during B:0.01% is following.
(23) it is characterized in that having outside described composition in quality % and also contain composition below the Ca:0.01% with the manufacture method of high strength stainless steel pipe as each described oil well in (13)～(22).
Description of drawings
Fig. 1 is the chart of expression crack length and formula (2) left side value relation.
Fig. 2 is the chart of expression crack length and ferrite content relation.
Fig. 3 is the chart of expression corrosion speed and formula (1) left side value relation.
Fig. 4 is the chart of influence that expression relates to the tissue of yield strength YS and Cr relation with contents.
Embodiment
At first, the basis that the oil well that limits among the present invention is formed with high strength stainless steel pipe describes.Below, the quality % that expression is formed only remembers and makes %.
More than the C:0.005%, below 0.05%
C is the important element that is related to martensitic stainless steel intensity, needs to make it to contain more than 0.005% among the present invention, when surpassing 0.05%, and the sensitization increase when containing the tempering that Ni causes.For reaching the purpose of sensitization when preventing this tempering, the amount that limits the C element in the present invention is in the scope more than 0.005%, below 0.05%.And from the viewpoint of erosion resistance, the C element is few more good more, and from guaranteeing the viewpoint of its intensity, the C element is The more the better, considers that its balance is preferred more than 0.03%, below 0.05%.
More than the Si:0.05%, below 0.5%
Si has been the element of reductor effect, and it is contained more than 0.05%, surpasses at 0.5% o'clock and makes its anti-CO
2Corrodibility reduces, and hot workability also reduces.Therefore, limit Si in the scope more than 0.05%, below 0.5%.And, preferred more than 0.1%, below 0.3%.
More than the Mn:0.2%, below 1.8%
Mn is the element that its intensity is increased, and for guaranteeing desired intensity, it is contained more than 0.2% in the present invention, when surpassing 1.8%, makes its toughness be subjected to bad influence.So limit Mn in the scope more than 0.2%, below 1.8%.And it is preferred more than 0.2%, below 1.0%.More preferably more than 0.2%, below 0.8%.
Below the P:0.03%
P makes anti-CO
2Corrodibility, anti-CO
2The element of stress corrosion cracking, anti-pitting attack and the common deterioration of the crackle of anti-sulphide stress corrosion property.Wish that in the present invention it reduces as far as possible, and extreme reduction can cause manufacturing cost to rise.P is limited to below 0.03%, and this scope is the industrial less expensive and scope that may implement, also is not make its anti-CO
2Corrodibility, anti-CO
2The scope of stress corrosion cracking, anti-pitting attack and the common deterioration of the crackle of anti-sulphide stress corrosion property.And preferably 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 is few as much as possible, can make steel pipe owing to be reduced to 0.005% with conventional operation when following, so qualification S is below 0.005%.Preferred below 0.002%.
More than the Cr:15.5%, below 18%
Cr is the element that forms the protection tunicle, improves erosion resistance, particularly helps to improve anti-CO
2Corrodibility, anti-CO
2The element of stress corrosion cracking.In the present invention, particularly, it is contained more than 15.5% from improving the viewpoint of the erosion resistance under the high temperature.On the other hand, when it surpasses 18%, the hot workability deterioration, intensity also reduces simultaneously.Therefore, in the present invention, with Cr be limited to more than 15.5%, 18% following scope.And, preferred more than 16.5%, below 18%, more preferably more than 16.6%, less than 18%.
More than the Ni:1.5%, below 5%
Ni be have make the protection tunicle firm, improve anti-CO
2Corrodibility, anti-CO
2The effect of stress corrosion cracking, anti-pitting attack and the crackle of anti-sulphide stress corrosion property, and increase the element of hardness of steel by solution strengthening.Thinking just has this effect when above containing 1.5%, and, the stability of martensitic stucture reduces when surpassing 5%, and intensity reduces.Therefore, Ni is limited in the scope more than 1.5%, below 5%.And it is preferred more than 2.5%, below 4.5%.
More than the Mo:1%, below 3.5%
Mo increases Cl
-Pitting attack resistivity element, need in the present invention to contain more than 1%.If less than 1% we can say that the erosion resistance under harsh high-temperature corrosion environment is insufficient.On the other hand, its content surpasses at 3.5% o'clock, and intensity reduces, and cost increases simultaneously.Therefore, Mo is limited in the scope more than 1%, below 3.5%.And preferably surpass 2%, below 3.5%.
More than the V:0.02%, below 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, when above 0.2% the time, and the toughness deterioration.Therefore, V is limited to more than 0.02%, below 0.2%.Preferred more than 0.02%, below 0.08%.
More than the N:0.01%, below 0.15%
N is the element that anti-pitting attack is improved significantly, and it is contained more than 0.01%, but its content surpasses at 0.15% o'clock, forms various nitride, the toughness deterioration.Therefore, N is limited to scope more than 0.01%, below 0.15%, and preferred more than 0.02%, below 0.08%.
Below the O:0.006%
O exists as oxide compound in steel, makes various characteristics be subjected to bad influence, is improved in order to make characteristic, and its content is low more good more.Particularly when O content surpasses 0.006% and more for a long time, 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 standard weave, can also contain more than the Al:0.002%, below 0.05%.Al is the element with very strong desoxydatoin, for reaching this effect it is contained more than 0.002%, and, its content surpasses at 0.05% o'clock makes its toughness be subjected to bad influence.Therefore, when containing Al, preferably it is limited to the scope more than 0.002%, below 0.05%.More preferably below 0.03%.When not adding Al, it allows to contain less than about 0.002% as unavoidable impurities.If Al is limited in less than about 0.002%, then has the advantage that low-temperature flexibility is 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.When content obvious in 0.5% its effect when above., 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 preferred more than 0.8%, below 2.5%, more preferably more than 0.5%, below 1.14%.
In addition, outside above-mentioned various compositions, can also contain below Nb:0.2% among the present invention, below the Ti:0.3%, below the Zr:0.2%, below the W:3%, more than a kind or 2 kinds of selection during B:0.01% is following.
Nb, Ti, Zr, W, B are the elements that intensity is increased, and can select as required, and Ti, Zr, W, B also are the elements that improves the anticorrosion stress-resistant crackle.This effect is containing more than the Nb:0.03%, and is more than the Ti:0.03%, more than the Zr:0.03%, more than the W:0.2%, remarkable when B:0.0005% is above.On the other hand, when each element exceeds following content Nb:0.2% respectively, Ti:0.3%, Zr:0.2%, W:3%, during B:0.01%, the toughness deterioration.Therefore, preferably be defined as following each constituent content: below the Nb:0.2%, below the Ti:0.3%, below the Zr:0.2%, below the W:3%, below the B:0.01%.
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 distortion of inclusion matrix is on every side dwindled, and has the hydrogen that makes inclusion and catches the effect that can reduce.This effect is 0.0005% remarkable when above at its content.Its content surpasses at 0.01% o'clock, causes CaO to increase anti-CO
2Corrodibility, anti-pitting attack reduction.Therefore, preferably Ca is limited to scope below 0.01%.
Among the present invention, adjust above-mentioned each composition, make it in above-mentioned scope, and satisfy following formula (1) and following formula (2).
Cr+0.65Ni+0.6Mo+0.55Cu-20C≥19.5 …(1)
Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 …(2)
Wherein, Cr, Ni, Mo, Cu, C, Si, Mn, N are the content (quality %) of each element
When the value on the calculating formula (1) and formula (2) left side, the element that does not contain calculates by zero %.
By adjusting the content of Cr, Ni, Mo, Cu, C, make it satisfy formula (1), contain CO at 230 ℃ of pyritous
2, Cl
-High-temperature corrosion environment under, its erosion resistance is improved significantly.And, from containing CO
2, Cl
-High-temperature corrosion environment under the viewpoint that improves of erosion resistance see that the value on formula (1) left side is preferably more than 20.0.
In addition, by adjusting the content of Cr, Mo, Si, C, Mn, Ni, Cu, N, make it satisfy formula (2), hot workability is improved.In the present invention, be improved, obviously reduce the content of P, S, O,, just reduce the content of P, S, O respectively and can not guarantee in order to make the needed sufficient hot workability of martensitic stainless steel weldless steel tube for making hot workability.In order to ensure making the needed sufficient hot workability of weldless steel tube, on the basis of the content that obviously reduces P, S, O, key is to adjust the content of Cr, Mo, Si, C, Mn, Ni, Cu, N, makes it satisfy formula (2).And from the viewpoint that hot workability improves, the value on formula (2) left side is preferably more than 12.0.
Surplus beyond the mentioned component is Fe and unavoidable impurities.
Oil well high strength stainless steel pipe of the present invention outside above-mentioned composition, preferably has martensitic phase as basic phase, contain volume fraction more than 10%, below 60%, preferably surpass 10%, the tissue of ferritic phase below 60%.
Steel pipe of the present invention, for guaranteeing its high strength, with martensitic stucture as standard weave.For not reducing its intensity its toughness is improved, is preferably formed martensitic phase as basic phase, contain as the volume fraction of second phase more than 10%, below 60%, preferably surpass 10%, the tissue of ferritic phase below 60%.Ferritic phase can not reach desired purpose when 10 volume % are following.On the other hand, when ferritic phase surpassed 60 volume %, its intensity reduced.Therefore, the volume fraction of ferritic phase is limited to more than 10%, below 60%, preferably is limited to the scope that surpasses below 10%, 60%.And, more preferably more than 15%, 50 volume %.As second phase beyond the ferritic phase, even contain the following austenite of 30 volume % mutually also without any problem.
Below, to the manufacture method of steel 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, the generally well-known method of ingot casting-cogging steel rolling method etc. is made the steel pipe starting material of billet etc.Then, these steel pipe starting material heating, with common Mannesmann-plug mill mode or with Mannesmann-mandrel mill mode, make steel pipe by hot-work, obtain the weldless steel tube of specified dimension, the weldless steel tube of making behind the pipe is preferably used the above speed of cooling cool to room temperature of air cooling.And, also can make weldless steel tube with the hot pressing of impact style.
Weldless steel tube with the composition in the invention described above scope after hot-work, with the above speed of cooling cool to room temperature of air cooling, can form the tissue of martensitic phase as basic phase., preferably after making steel pipe, with the above speed of cooling cooling of air cooling, then carry out following quench treatment: the temperature of reheat to 850 ℃, the speed of cooling above with air cooling is cooled to below 100 ℃, preferably cool to room temperature.By above-mentioned processing, can form the fine high tenacity martensitic stucture of the ferritic phase that contains appropriate amount.
If quenching temperature is less than 850 ℃, and the martensite part is not fully quenched, and its intensity has the tendency of reduction.Therefore, the preferred temperature more than 850 ℃ of the Heating temperature of quench treatment.
Implement the weldless steel tube of quench treatment, preferably then implement following temper: be heated to the temperature below 700 ℃, cool off with the speed of cooling more than the air cooling, by be heated to below 700 ℃, preferred more than 400 ℃ temperature and carry out tempering, it is organized into to by tempered martensite mutually or the tissue that constitutes mutually of a spot of ferritic phase and austenite, thereby becomes the weldless steel tube with desired high strength, high tenacity and superior corrosion resistance.
And, can carry out temper, only implement above-mentioned temper.
So far, be to be the explanation of example 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, can make Electric Welded Steel Pipe, UOE steel pipe as the oil well steel pipe.
Use has the steel pipe starting material of forming in the invention described above scope, steel pipe beyond the weldless steel tube that obtains according to common manufacturing process, as Electric Welded Steel Pipe, UOE steel pipe, for made steel pipe, preferably carry out above-mentioned quenching-temper: after the temperature of reheat to 850 ℃, be cooled to below 100 ℃ with the speed of cooling more than the air cooling, the quench treatment of preferred cool to room temperature and then be heated to below 700 ℃, preferred temperature more than 400 ℃, carry out the refrigerative temper with the speed of cooling more than the air cooling.
Embodiment
Be to illustrate in greater detail the present invention below according to embodiment.
Embodiment 1
Behind liquid steel degassing with the composition shown in the table 1, cast the steel ingot (steel pipe starting material) of 100kg, utilize the seamless milling train of model to make steel pipe by hot-work, make the cold or water-cooled of the laggard line space of steel pipe, make the weldless steel tube of external diameter 83.8mm * wall thickness 12.7mm (3.3in * wall thickness 0.5in).
To the weldless steel tube that obtains, to make under the cold state of the laggard line space of steel pipe, visual research surfaces externally and internally has flawless generation, estimates hot workability.During crackle more than there is long 5mm in the pipe front/rear end, be defined as crackle, in addition situation has been defined as flawless.
And, cut out the sample starting material from the weldless steel tube that obtains, behind heating 30min under 920 ℃ the temperature, carry out water-cooled (from the average cooling rate that is cooled to 500 ℃ more than 800 ℃ be 10 ℃/s).Implement the temper of 580 ℃ * 30min again.From implementing as mentioned above on the sample starting material after the quenching-temper, the sample of taking tissues observed to use, the sample that tissues observed is used corrodes in chloroazotic acid, with scanning electronic microscope (1000 times) tissue is made a video recording, that uses that image analysis apparatus calculates ferritic phase organizes per-cent (volume %).
In addition, the residual austenite phase organize per-cent, use X-ray diffraction method to measure.From having implemented to take to measure the sample of usefulness on the sample starting material after quenching-temper, measure the X-ray diffraction integrated intensity of (221) face of (220) face, the α of γ by X-ray diffraction, convert with following formula.
γ (volume fraction)=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
And the per-cent of martensitic phase calculates as the surplus beyond these phases.
And, from the sample starting material of implementing quenching-temper, take API arc tension specimen, implement tension test, obtain tensile properties (yield strength YS, tensile strength TS).
Further, from the sample starting material of implementing quenching-temper,, make the corrosion sample of thick 3mm * wide 30mm * long 40mm, implement corrosion test by mechanical workout.
Corrosion test is the experimental liquid in remaining in autoclave: 20% the NaCl aqueous solution (liquid temperature: the CO under 230 ℃, 100 normal atmosphere
2In the gas atmosphere) in, the immersion corrosion sample was 2 weeks between soak period.For the sample after the corrosion test, measure its weight, according to the reduction of the sample weight before and after the corrosion test, calculate and obtain corrosion speed.And, 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.Be defined as pitting attack observing the pitting attack of diameter more than 0.2mm, in addition situation has been defined as no pitting attack.The gained result is as shown in table 2.
Example of the present invention is not all found steel tube surface generation crackle, and it has the high strength of yield strength YS more than 654MPa the steel pipe of formation, and corrosion speed is also little, does not have pitting attack to take place, hot workability and containing CO
2And temperature is the excellent corrosion resistance under 230 ℃ the harsh high-temperature corrosion environment.And, containing CO owing to the ferritic phase that contains more than 5%
2And temperature is to have superior corrosion resistance under 230 ℃ the harsh high-temperature corrosion environment, and has the high strength of yield strength YS more than 654MPa.
In contrast, the comparative example beyond the scope of the present invention, crackle takes place in its surface, and hot workability reduces, or the corrosion speed increase, the origination point corrosion, erosion resistance reduces.Particularly do not satisfy the comparative example of formula (2), its hot workability reduces, and steel tube surface produces damage.And ferritic amount is under the situation beyond the suitable scope of the present invention, and its intensity reduces, and can not satisfy the high strength of yield strength YS more than 654MPa.
Steel pipe starting material with the represented composition of table 1 (steel No.B, No.S), make steel pipe by hot-work, it is cold to make the laggard line space of steel pipe, becomes the weldless steel tube of external diameter 83.8mm * wall thickness 12.7mm (3.3in * wall thickness 0.5in).Cut out the sample starting material from the weldless steel tube that obtains, implement quenching-temper or temper as shown in table 3.
From the sample starting material of implementing quenching-temper, equally take sample that tissues observed uses, measure the sample of usefulness with embodiment 1, calculate ferritic phase organize per-cent (volume %), residual austenite organize per-cent (volume %), martensitic phase organize per-cent (volume %).
And, from the sample starting material of implementing quenching-temper, take API arc tension specimen, identical with embodiment 1, implement tension test, obtain tensile properties (yield strength YS, tensile strength TS).Further, identical with embodiment 1 from the sample starting material of implementing quenching-temper, by mechanical workout, make the corrosion sample of thick 3mm * wide 30mm * long 40mm, implement corrosion test, obtain corrosion speed.And, identical with embodiment 1, to observe specimen surface and have or not pitting attack to take place, judgement criteria is identical with embodiment 1.The gained result is as shown in table 3.
Example of the present invention all is to have the high strength of yield strength YS more than 654MPa, and corrosion speed is also little, does not have pitting attack to take place, hot workability and containing CO
2And temperature is the steel pipe of the excellent corrosion resistance under 230 ℃ the harsh high-temperature corrosion environment.In example of the present invention, under the situation beyond the suitable scope of the present invention, its intensity or erosion resistance, hot workability have the tendency of reduction.
Embodiment 3
After molten steel with composition represented in the table 4 degassed, cast the steel ingot of 100kg, utilize the seamless milling train of model to make steel pipe, cool off (air cooling) after making steel pipe, make it become the weldless steel tube of external diameter 83.8mm * wall thickness 12.7mm (3.3in * wall thickness 0.5in) by hot-work.
To the weldless steel tube that obtains, identical with embodiment 1 under the state of making steel pipe postcooling (air cooling), visual research steel pipe surfaces externally and internally has flawless generation, estimates hot workability.And judgement criteria is identical with embodiment 1.
And, cut out the sample starting material from the weldless steel tube that obtains, behind heating 30min under 900 ℃ the temperature, carry out water-cooled.Implement the temper of 580 ℃ * 30min again.From such enforcement on the sample after quenching-temper, sample, the mensuration sample of taking tissues observed to use, the sample that tissues observed is used makes its corrosion in chloroazotic acid, with scanning electronic microscope (1000 times) tissue is made a video recording, that uses that image analysis apparatus calculates ferritic phase organizes per-cent (volume %).From having implemented on the sample starting material after quenching-temper, take to measure and use sample, identical with embodiment 1, mensuration residual austenite, martensitic phase organize per-cent (volume %).
And, from the sample starting material of implementing quenching-temper, take API arc tension specimen, implement tension test, obtain tensile properties (yield strength YS, tensile strength TS).Further, from the sample starting material of implementing quenching-temper, take V notched specimen (thickness: 5mm), implement to look into Charpy impact test, ask the absorption energy vE-in the time of-40 ℃ according to the regulation of JIS Z 2242 according to the regulation of JIS Z 2202
40(J).
Further, from the sample starting material of implementing quenching-temper,, make the corrosion sample of thick 3mm * wide 30mm * long 40mm, implement corrosion test by mechanical workout.And a part of steel pipe is not carried out quench treatment, only carries out temper.
Corrosion test is the experimental liquid in remaining in autoclave: 20% the NaCl aqueous solution (liquid temperature: the CO under 230 ℃, 100 normal atmosphere
2Gas atmosphere) in, the immersion corrosion sample was 2 weeks between soak period.For the sample after the corrosion test, measure its weight, according to the reduction of the sample weight before and after the corrosion test, calculate and obtain corrosion speed.In addition, about anti-pitting attack, steel pipe is soaked in 40% CaCl
2In (liquid temperature: 70 ℃) solution, soaked 24 hours, research has or not the generation of pitting attack.Be defined as pitting attack observing the pitting attack of diameter more than 0.1mm, in addition situation has been defined as no pitting attack.The gained result is as shown in table 5.
Example of the present invention is not all found steel tube surface generation crackle, and is to have the high strength of yield strength YS more than 654MPa, and corrosion speed is also little, does not have pitting attack to take place, hot workability and containing CO
2And temperature is the steel pipe of the excellent corrosion resistance under 230 ℃ the harsh high-temperature corrosion environment.Owing to contain the ferritic phase more than 5%, containing CO
2And temperature is under 230 ℃ the harsh high-temperature corrosion environment, to have superior corrosion resistance, and have yield strength YS in the high strength more than the 654MPa and the absorption when having at-40 ℃ can be more than 50J high tenacity.And Al content is higher among steel pipe No.13, the No.14, and toughness has some reductions, the origination point corrosion, but its degree is slight, the not enough 0.2mm of diameter.
In contrast, the comparative example beyond the scope of the invention, crackle takes place in its surface, and hot workability reduces, or the corrosion speed increase, the origination point corrosion, erosion resistance reduces.Particularly do not satisfy the comparative example of formula (2), its hot workability reduces, and steel tube surface is damaged.And ferritic amount is under the situation beyond the suitable scope of the present invention, and its intensity reduces, and can not satisfy the high strength of yield strength YS more than 654MPa.
The possibility of utilizing on the industry
According to the present invention, can be cheap and stably be manufactured on and contain CO2、Cl
-Harsh height Have good corrosion resistance under the environment of temperature corrosion, have high strength or also have high-ductility The oil well stainless steel tube of property. Industrially prove effective especially. According to the present invention, also have as follows Advantage: after making steel pipe, only heat-treat and just can obtain enough as oil well steel pipe Intensity.
Claims (23)
1. the oil well high strength stainless steel pipe of an excellent corrosion resistance is characterized in that, its composition contains in quality %:
More than the C:0.005%, below 0.05%,
More than the Si:0.05%, below 0.5%,
More than the Mn:0.2%, below 1.8%,
Below the P:0.03,
Below the S:0.005%,
More than the Cr:15.5%, below 18%,
More than the Ni:1.5%, below 5%,
More than the Mo:1%, below 3.5%,
More than the V:0.02%, below 0.2%,
More than the N:0.024%, below 0.15%,
Below the O:0.006%,
And satisfy following formula (1) and formula (2), surplus is made of Fe and unavoidable impurities, and yield strength surpasses 654MPa,
Cr+0.65Ni+0.6Mo+0.55Cu-20C≥19.5…(1)
Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5…(2)
Wherein, Cr, Ni, Mo, Cu, C, Si, Mn, N are the quality % content of each element.
2. oil well high strength stainless steel pipe as claimed in claim 1 is characterized in that, has outside described composition in quality % also to contain composition more than the Al:0.002%, below 0.05%.
3. oil well high strength stainless steel pipe as claimed in claim 1 or 2 is characterized in that, in quality %, the content of described C is more than 0.03%, below 0.05%.
4. oil well high strength stainless steel pipe as claimed in claim 1 or 2 is characterized in that, the content of described Cr more than 16.6%, less than 18%.
5. oil well high strength stainless steel pipe as claimed in claim 1 or 2 is characterized in that, in quality %, the content of described Mo is more than 2%, below 3.5%.
6. oil well high strength stainless steel pipe as claimed in claim 1 or 2 is characterized in that, has outside described composition in quality % also to contain composition more than the Cu:0.5%, below 3.5%.
7. oil well high strength stainless steel pipe as claimed in claim 6 is characterized in that, in quality %, the content of described Cu is more than 0.5%, below 1.14%.
8. oil well high strength stainless steel pipe as claimed in claim 1 or 2, it is characterized in that, have outside described composition, also contain in quality % be selected from more than the Nb:0.03%, below 0.2%, more than the Ti:0.03%, below 0.3%, Zr:0.03% is above, below 0.2%, W:0.2% is above, below 3%, B:0.0005% is above, the composition more than a kind or 2 kinds in below 0.01%.
9. oil well high strength stainless steel pipe as claimed in claim 1 or 2 is characterized in that, has outside described composition in quality % also to contain composition more than the Ca:0.0005%, below 0.01%.
10. oil well high strength stainless steel pipe as claimed in claim 1 or 2 is characterized in that, has with martensitic phase as basic phase, also contains the tissue that volume fraction is the ferritic phase more than 10%, below 60%.
11. oil well high strength stainless steel pipe as claimed in claim 10 is characterized in that, the volume fraction of described ferritic phase is more than 15%, below 50%.
12. as claim 10 or 11 described oil well high strength stainless steel pipes, it is characterized in that, describedly organize that also to contain volume fraction be austenite phase below 30%.
13. the oil well of the excellent corrosion resistance manufacture method of high strength stainless steel pipe, it is characterized in that, to have in quality % and contain more than the C:0.005%, below 0.05%, more than the Si:0.05%, below 0.5%, more than the Mn:0.2%, below 1.8%, below the P:0.03, below the S:0.005%, more than the Cr:15.5%, below 18%, more than the Ni:1.5%, below 5%, more than the Mo:1%, below 3.5%, more than the V:0.02%, below 0.2%, more than the N:0.01%, below 0.15%, below the O:0.006%, and satisfy following formula (1) and formula (2), the steel pipe starting material of forming that surplus is made of Fe and unavoidable impurities, make the steel pipe of specified dimension, after the temperature more than this steel pipe reheat to 850 ℃, the speed of cooling above with air cooling is cooled to below 100 ℃, then, enforcement is heated to the quenching-temper of the temperature below 700 ℃
Cr+0.65Ni+0.6Mo+0.55Cu-20C≥19.5…(1)
Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5…(2)
Wherein, Cr, Ni, Mo, Cu, C, Si, Mn, N are the quality % content of each element.
14. the oil well as claimed in claim 13 manufacture method of high strength stainless steel pipe, it is characterized in that, described steel pipe starting material are heated, make pipe by hot-work, after making pipe, be cooled to room temperature with the speed of cooling more than the air cooling, 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 oil wells usefulness high strength stainless steel pipes is characterized in that, replaces described quenching-temper, implements to be heated to the temper of the temperature below 700 ℃.
16. with the manufacture method of high strength stainless steel pipes, it is characterized in that having outside described composition in quality % and also contain composition more than the Al:0.002%, below 0.05% as claim 13 or 14 described oil wells.
17. the manufacture method as claim 13 or 14 described oil wells usefulness high strength stainless steel pipes is characterized in that in quality %, the content of described C is more than 0.03%, below 0.05%.
18., it is characterized in that with the manufacture method of high strength stainless steel pipes as claim 13 or 14 described oil wells, the content of described Cr more than 16.6%, less than 18%.
19. the manufacture method as claim 13 or 14 described oil wells usefulness high strength stainless steel pipes is characterized in that in quality %, the content of described Mo is more than 2%, below 3.5%.
20. with the manufacture method of high strength stainless steel pipes, it is characterized in that having outside described composition in quality % and also contain composition more than the Cu:0.5%, below 3.5% as claim 13 or 14 described oil wells.
21. oil well as claimed in claim 20 is characterized in that with the manufacture method of high strength stainless steel pipe in quality %, the content of described Cu is more than 0.5%, below 1.14%.
22. manufacture method as claim 13 or 14 described oil wells usefulness high strength stainless steel pipes, it is characterized in that, have outside described composition, also contain in quality % be selected from more than the Nb:0.03%, below 0.2%, more than the Ti:0.03%, below 0.3%, Zr:0.03% is above, below 0.2%, W:0.2% is above, below 3%, B:0.0005% is above, the composition more than a kind or 2 kinds in below 0.01%.
23. with the manufacture method of high strength stainless steel pipes, it is characterized in that having outside described composition in quality % and also contain composition more than the Ca:0.0005%, below 0.01% as claim 13 or 14 described oil wells.
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| JP295163/2003 | 2003-08-19 | ||
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| JP071640/2004 | 2004-03-12 | ||
| JP135974/2004 | 2004-04-30 | ||
| JP210904/2004 | 2004-07-20 |
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