CN101061245A - Martensitic stainless steel - Google Patents

Martensitic stainless steel Download PDF

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CN101061245A
CN101061245A CNA2005800396559A CN200580039655A CN101061245A CN 101061245 A CN101061245 A CN 101061245A CN A2005800396559 A CNA2005800396559 A CN A2005800396559A CN 200580039655 A CN200580039655 A CN 200580039655A CN 101061245 A CN101061245 A CN 101061245A
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steel
stainless steel
martensitic stainless
tempering
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CN100549204C (en
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高部秀树
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Sumitomo Metal Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C21D1/25—Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite

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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
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Abstract

A martensitic stainless steel which has a chemical composition, in mass %, that C: 0.001 to 0.01 %, Si: 0.5 % or less, Mn: 0.1 to 3.0 %, P: 0.04 % or less, S: 0.01 % or less, Cr: 10 to 15 %, Ni: 4 to 8 %, Mo: 2.8 to 5.0 %, Al: 0.001 to 0.10 %, N: 0.07 % or less, Ti: 0 to 0.25 %, V: 0 to 0.25 %, Nb: 0 to 0.25 %, Zr: 0 to 0.25 %, Cu: 0 to 1.0 %, Ca: 0 to 0.005 %, Mg: 0 to 0.005 %, La: 0 to 0.005 %, Ce: 0 to 0.005 %, and the balance: Fe and impurities, with a proviso that the following formulae (1) and (2) are satisfied, and exhibits a yield stress of 758 to 860 MPa. 922.6 - 554.5C - 50.9Mn +2944.8P + 1.056Cr - 81.1Ni + 95.8Mo - 125.1Ti - 1584.9Al - 376.1N = 600 (1) 30C + 0.5Mn + Ni + 0.5Cu - 1.5Si - Cr - Mo + 7.9 = 0 (2) The above martensitic stainless steel can achieve a yield stress of 758 to 860 MPa with a range of tempering temperature being broader than that in the case of a conventional martensitic stainless steel.

Description

Martensitic stainless steel
Technical field
The present invention relates to martensitic stainless steel, more particularly, relate to the martensitic stainless steel that in the corrosive environment that contains the such corrosives of hydrogen sulfide, carbonic acid gas, chlorion, uses.
Background technology
Along with the deep-wellization of oil well, gas well, require to have high strength and high tenacity with the martensitic stainless steel that steel use as oil wells such as oil well pipes.For this reason, developing yielding stress (0.2% yield strength) and be 758～860MPa (below, be referred to as the 110ksi level) martensitic stainless steel, have the above high-intensity martensitic stainless steel of 110ksi level.
The martensitic stainless steel that oil well is used also will have the high corrosion resistance of anti-SCC (stress corrosion fracture) property, anti-SSC (sulfuration stress corrosion) property.This is because oil well, gas well are corrosive environments, contains hydrogen sulfide, carbonic acid gas, the such corrosives of chlorion.That is to say that the martensitic stainless steel that requires oil well to use has high strength, high tenacity and high corrosion resistance.
TOHKEMY 2003-3243 communique discloses the martensitic stainless steel with high strength and high corrosion resistance.Owing to the martensitic stainless steel that is disclosed in the document makes Mo content in quality % is more than 1.5%, is higher than the anti-SSC of martensitic stainless steel in the past so have.
But under the high situation of Mo content, the scope (below, be referred to as tempering range) that can obtain the tempering temperature of 110ksi level intensity becomes very little.Fig. 1 is the yielding stress of the high martensitic stainless steel of expression Mo content (below, be referred to as high Mo martensitic stainless steel) and the figure of the relation between the tempering temperature.In quality %, the high Mo martensitic stainless steel among Fig. 1 contains 0.016% C, 11.8% Cr, 7.2% Ni, 2.9% Mo, and all the other compositions are Fe and impurity.With reference to Fig. 1, the obliquity of the tempering curve C10 in yielding stress is the scope of 758～860MPa is bigger.Therefore, for the intensity that makes high Mo martensitic stainless steel reaches the 110ksi level, tempering temperature must be set in the about 580 ℃～about 600 ℃ scope.That is to say that the tempering range Δ T that is used to make intensity reach the 110ksi level is very little.
If T is little for the tempering range Δ, will reduce productivity.Usually, make the high Mo martensitic stainless steel of hundreds of ton continuously, under these circumstances, high Mo martensitic stainless steel be with a plurality of in 1 system steel operation resulting molten steel (heat) produced, and the chemical ingredients of each resulting molten steel in 1 system steel operation is not quite identical, has some variations.Under the less situation of tempering range Δ T,, must when changing to some extent, chemical ingredients change tempering range for the intensity that makes steel reaches the 110ksi level.In a word, for the intensity that makes steel reaches the 110ksi level, need make the setting that resulting molten steel changes tempering temperature in the steel operation at 1 time to each.The change setting tempering temperature can reduce productivity like this.
In addition, as patent documentation related to the present invention, can exemplify out international open WO2004/57050.
Summary of the invention
The object of the present invention is to provide a kind of martensitic stainless steel, the tempering range of the yielding stress that can obtain 758～860MPa of this martensitic stainless steel is big.
The present inventor draws following opinion through all experiments and research.
(A) if adopt the A that improves martensitic stainless steel C1The chemical ingredients of transformation temperature, then yielding stress is the tempering range expansion of 758～860MPa.This is because if A C1Transformation temperature is low, then generates austenite in high tempering, thereby causes steel strength to reduce.
(B) not only to improve A C1Transformation temperature also will reduce C content.Thus, yielding stress is that the tempering range of 758～860MPa further enlarges.This is because C content is high more, and the obliquity of the tempering curve in yielding stress is the scope of 758～860MPa is just big more.
(C) if reduce C content, then generate delta ferrite easily, influence the intensity and the toughness of steel.Be lower than at outside air temperature for the martensitic stainless steel that makes the 110ksi level under 0 ℃ the environment and also can use, except needs possess high strength, also need to possess high tenacity.Even improve A if adopt C1Transformation temperature and reduce C content also can make the chemical ingredients of organizing formation of martensite of steel, then can suppress the generation of delta ferrite, can keep the intensity of 110ksi level can prevent that again toughness from reducing.
Study based on above opinion, found that if to make C content be 0.01% below and satisfy formula (1) and formula (2), then can make yielding stress is that the tempering range that compares in the past of the tempering range of 758～860MPa is big.
922.6-554.5C-50.9Mn+2944.8P+1.056Cr-81.1Ni+95.8Mo-125.1Ti-1584.9Al-376.1N≥600(1)
30C+0.5Mn+Ni+0.5Cu-1.5Si-Cr-Mo+7.9≥0(2)
At this, the coefficient in the formula is the content (quality %) of each element.
The left side of formula (1) (below, make that the left side of formula (1)=F1) is the A of prediction martensitic stainless steel of the present invention C1The formula of transformation temperature.As previously mentioned, if improve A C1Transformation temperature then can be suppressed at and separate out retained austenite in the tempering, therefore can prevent that yielding stress from sharply descending.In other words, can reduce the obliquity that yielding stress is the tempering curve in the scope of 758～860MPa.
Satisfying F1 〉=600, is because will carry out temper with the tempering temperature below 600 ℃.If tempering temperature, then can cause tiny carbide, intermetallic compound alligatoring in the steel more than 600 ℃, intensity reduces on the contrary, and toughness also can reduce.In order to make tempering temperature below 600 ℃, the value of F1 is to get final product more than 600 ℃.
Formula (2) is in order to make the formula of the steel formation of martensite after the tempering.If make the content of the content of austenite former C, Mn, Ni and ferrite former Si, Cr, Mo satisfy the relation of formula (2), then tissue becomes martensite, can prevent to generate delta ferrite.Therefore can prevent that intensity from reducing, and can keep high tenacity.
In addition, do not contain in martensitic stainless steel under the situation of Ti, Cu of optional element, the coefficient that " Ti " in formula (1) and the formula (2) reaches " Cu " is " 0 ".
If satisfy these formulas, then can obtain the such tempering curve of curve C 1 as shown in Figure 2, the obliquity that also can make the tempering curve in the yielding stress scope of 758～860MPa is littler than the obliquity of tempering curve in the past.Therefore, the yielding stress of curve C 1 is that the tempering range Δ T1 of 758～860MPa is that the tempering range Δ T2 of 758～860MPa is big than the yielding stress of in the past tempering curve C2.So, can suppress in operation the change that tempering temperature is set and the productivity that causes reduces.
The present inventor finishes following invention based on above opinion.
In quality %, martensitic stainless steel of the present invention contains C:0.001～0.01%, below the Si:0.5%, Mn:0.1～3.0%, below the P:0.04%, below the S:0.01%, Cr:10～15%, Ni:4～8%, Mo:2.8～5.0%, Al:0.001～0.10%, below the N:0.07%, Ti:0～0.25%, V:0～0.25%, Nb:0～0.25%, Zr:0～0.25%, Cu:0～1.0%, Ca:0～0.005%, Mg:0～0.005%, La:0～0.005%, Ce:0～0.005%, all the other compositions are made of Fe and impurity, satisfy formula (1) and formula (2), have the yielding stress of 758～860MPa.
922.6-554.5C-50.9Mn+2944.8P+1.056Cr-81.1Ni+95.8Mo-125.1Ti-1584.9Al-376.1N≥600(1)
30C+0.5Mn+Ni+0.5Cu-1.5Si-Cr-Mo+7.9≥0(2)
At this, the coefficient in the formula is the content (quality %) of each element.In addition, under the situation that does not contain optional element Ti, Cu, the coefficient that " Ti " in formula (1) and the formula (2) reaches " Cu " is " 0 ".In addition, making yielding stress is 0.2% of yield strength.
Martensitic stainless steel of the present invention can be 0.01% to reduce the obliquity of tempering curve to get off by making C content.And, owing to satisfy formula (1), therefore can make A C1Transformation temperature is higher than the A of steel in the past C1Transformation temperature.Therefore, the obliquity of tempering curve diminishes, and yielding stress is that the tempering range of 758～860MPa is bigger than in the past.
And, can prevent intensity less than 110ksi, and can keep high tenacity by satisfying formula (2).In addition, because Mo content height, so have high corrosion resistance.
Martensitic stainless steel of the present invention preferably contains more than one in Ti:0.005～0.25%, V:0.005～0.25%, Nb:0.005～0.25%, Zr:0.005～0.25%.
Martensitic stainless steel of the present invention preferably contains Cu:0.05～1.0%.
Martensitic stainless steel of the present invention preferably contains more than one in Ca:0.0002～0.005%, Mg:0.0002～0.005%, La:0.0002～0.005%, Ce:0.0002～0.005%.
In this case, can improve the hot workability of martensitic stainless steel.In addition, even contain these elements, also can not influence the effect of foregoing invention.
Description of drawings
Fig. 1 is the figure that represents the yielding stress and the relation between the tempering temperature of high Mo martensitic stainless steel in the past.
Fig. 2 is sample 1 and the yielding stress of sample 14 and the figure of the relation between the tempering temperature of expression embodiments of the invention.
Embodiment
Below the embodiment that present invention will be described in detail with reference to the accompanying.To the identical Reference numeral of part mark identical or suitable among the figure, and omit its repeat specification.
1. chemical ingredients
The martensitic stainless steel of embodiments of the present invention contains following composition.Below, the % of element is meant quality %.
C：0.001～0.01％
If contain excessive C, the obliquity steepening of tempering curve can't stably obtain to have the steel of the yielding stress of 758～860MPa.Therefore should control C content lower.On the other hand, if C content can improve manufacturing cost less than 0.001%.Therefore, making C content is 0.001～0.01%.Preferred C content is 0.001～0.008%.
Below the Si:0.5%
Si is effective reductor.On the other hand, if make hardening of steel and contain excessive Si, then can cause the toughness and the processibility variation of steel.On the other hand, Si is a ferrite former, so hinder the formation of martensite of steel.Therefore, making Si content is below 0.5%.Preferred Si content is below 0.3%.
Mn：0.1～3.0％
Mn is of value to the hot workability that improves steel.And Mn is an austenite former, is of value to the formation of martensite of tissue.But, then cause toughness to reduce if contain excessive Mn.Therefore, making Mn content is 0.1～3.0%.Preferred Mn content is 0.3～1.0%.
Below the P:0.04%
P is an impurity.Because P can cause producing SSC, so will control P content lower as far as possible.Particularly, making P content is below 0.04%.
Below the S:0.01%
S is an impurity.S can reduce the hot workability of steel.So, control S content lower as far as possible.Particularly, making S content is below 0.01%.
Cr：10～15％
Cr is of value to the erosion resistance of raising steel in moistening carbon dioxide environment.On the other hand, because Cr is a ferrite former, so, cause the intensity of steel and toughness to reduce if containing excessive Cr then is difficult to form tempered martensite.Therefore making Cr content is 10～15%.Preferred Cr content is 11～14%.
Ni：4～8％
Ni is an austenite former, is to organize formation of martensite and the element that needs in order to make after the tempering.Cross when low at Ni content, the tissue after the tempering contains more ferrite.And when the Ni too high levels, the tissue after the tempering contains more austenite.So making Ni content is 4～8%.Preferred Ni content is 4～7%.
Mo：2.8～5.0％
Mo is of value to the anti-SSC that improves steel and the important element of intensity.In the martensitic stainless steel of present embodiment, make the following of Mo content be limited to 2.8% in order to obtain high anti-SSC.On the other hand, because Mo is a ferrite former, add the formation of martensite that excessive Mo hinders tissue.Therefore, make Mo content on be limited to 5.0%.Preferred Mo content is 2.8～4.0%.
Al：0.001～0.10％
Al is effective reductor.But, if Al content is too much, then can generate more inclusion, reduce the erosion resistance of steel.Therefore, making Al content is 0.001～0.10%.Preferred Al content is 0.001～0.06%.
Below the N:0.07%
N can form nitride and reduce the erosion resistance of steel.Therefore, N content is made as below 0.07%.
In addition, all the other compositions are made of Fe and impurity.Impurity is to contain because of various factors in the manufacturing processed etc.
As required, the martensitic stainless steel of present embodiment also can contain more than one among Ti, V, Nb, the Zr.
Ti：0～0.25％
V：0～0.25％
Nb：0～0.25％
Zr：0～0.25％
Ti, V, Nb, Zr are optional element.These elements are used for fixing C, reduce the inequality of intensity.On the other hand, if contain these excessive elements, then hinder the formation of martensite of organizing after the tempering.Therefore, preferably making the content of these elements respectively is 0～0.25%.Preferred content respectively is 0.005～0.25%, and preferred content respectively is 0.005～0.20%.
As required, the martensitic stainless steel of present embodiment also can contain Cu.
Cu：0～1.0％
Cu is an optional element.Cu is the same with Ni to be austenite former, is of value to the formation of martensite of organizing after the tempering.On the other hand, if contain the hot workability that excessive Cu then can reduce steel.Therefore, Cu content is made as 0～1.0%.Preferred Cu content is 0.05～1.0%.
As required, the martensitic stainless steel of present embodiment also can contain more than one among Ca, Mg, La, the Ce.
Ca：0～0.005％
Mg：0～0.005％
La：0～0.005％
Ce：0～0.005％
Ca, Mg, La, Ce are optional element.These elements are of value to the hot workability that improves steel.On the other hand,, then can cause generating thick oxide compound, reduce the erosion resistance of steel if contain these excessive elements.Therefore, making the content of these elements respectively is 0～0.005%.Preferred content is to be respectively 0.0002～0.005%.In these elements, the element that is particularly useful for the hot workability that improves steel is Ca and La.
2. manufacture method
The steel of the above-mentioned chemical ingredients of melting carries out refining by known refining procedure.By continuous metal cast process molten steel is made continuously cast then.So-called continuously cast for example is slab, Steel Bloom, billet.Perhaps molten steel is made steel ingot by ingot casting method.
Slab, Steel Bloom, steel ingot are carried out hot-work and make billet.At this moment, can make billet, also can make billet by forge hot by hot rolling.
To using continuous casting or the resulting billet of hot-work to carry out hot-work and make oil well pipe.For example implement Mannesmann's method as hot-work.As hot-work can date of execution Nei-hot extrusion such as (Ugine-Sejournet) mode in you of Sai scholar, also can implement hammer welded pipe manufacture method such as Ehrhardt method mode.Oil well pipe after the hot-work is implemented quenching and tempering to be handled.Carry out quench treatment with known method.For example, making quenching temperature is 900 ℃～950 ℃.But, also can adopt other temperature ranges.
In temper, be limited to 500 ℃ under the preferred tempering temperature.On the other hand,, then can separate out retained austenite, can't make yielding stress reach 758～860MPa if tempering temperature is too high.Therefore, be limited to 600 ℃ on the preferred tempering temperature.
The martensitic stainless steel of embodiments of the present invention also satisfies with following formula (1) and formula (2).
922.6-554.5C-50.9Mn+2944.8P+1.056Cr-81.1Ni+95.8Mo-125.1Ti-1584.9Al-376.1N≥600(1)
30C+0.5Mn+Ni+0.5Cu-1.5Si-Cr-Mo+7.9≥0(2)
If satisfy formula (1), then A C1Transformation temperature raises, so can reduce the obliquity of the tempering curve in yielding stress is the scope of 758～860MPa.And, then can promote the formation of martensite organized if satisfy formula (2).Therefore, if satisfy formula (1) and formula (2), the tempering range of yielding stress that then can enable to obtain 758～860MPa is bigger than in the past.Therefore, can suppress in operation the change that tempering temperature is set and the productivity that causes reduces.
Can also obtain as the oil well necessary high tenacity of steel by satisfying formula (2).
In addition, in martensitic stainless steel, do not contain under the situation of optional element Ti, Cu, " Ti " in formula (1) and the formula (2), " Cu " coefficient is " 0 ".
In the above description martensitic stainless steel is processed into steel pipe, also martensitic stainless steel can be processed into steel plate.
Embodiment 1
Manufacturing has the sample of the chemical ingredients shown in the table 1, and having investigated yielding stress in each sample is the tempering range of 758～860MPa.And the toughness and the erosion resistance of each sample have been investigated.
Table 1
Sequence number Chemical ingredients (unit is in quality %, and rest part is Fe and impurity) F1 F2
C Sl Mn P S Cu Cr Nl Mo sol.AL N Nb V Tl Zr Ca Mg La Ce
Steel of the present invention 1 0.006 0.14 0.46 0.012 0.0008 0.02 11.79 6.79 2.91 0.020 0.0053 0.002 0.11 0.075 0 0 0 0 0 628.7 0.20
2 0.006 0.14 0.47 0.012 0.0008 0.02 11.75 6.78 2.90 0.027 0.0030 0.002 0.06 0.081 0 0 0 0 0 617.0 0.25
3 0.007 0.17 0.40 0.014 0.0011 0.02 11.88 6.90 2.95 0.029 0.0075 0.002 0.05 0 0 0.0007 0 0 0 626.4 0.14
4 0.006 0.15 0.47 0.012 0.0008 0.26 11.79 6.72 2.91 0.025 0.0038 0.002 0.06 0.079 0 0 0 0 0 626.0 0.24
5 0.006 0.20 0.46 0.011 0.0010 0.03 11.88 7.01 3.12 0.035 0.0053 0 0.06 0.093 0 0 0 0 0 602.1 0.03
6 0.007 0.16 0.47 0.012 0.0009 0.93 11.78 6.37 2.90 0.025 0.0037 0.002 0.06 0.079 0.0003 0 0 0 0 652.9 0.26
7 0.008 0.14 0.30 0.017 0.0010 0 11.00 7.90 4.80 0.035 0.0060 0 0.04 0.100 0 0 0.0006 0 0 713.5 0.18
8 0.004 0.15 0.45 0.011 0.0010 0 11.90 7.98 3.80 0.025 0.0099 0 0.05 0.088 0 0 0 0 0 604.9 0.30
9 0.006 0.16 0.46 0.012 0.0008 0.03 11.90 6.79 2.91 0.020 0.0501 0.002 0.11 0.075 0 0 0 0.0009 0 611.9 0.06
10 0.006 0.14 0.46 0.012 0.0010 0.02 11.70 6.56 2.91 0.020 0.0450 0 0.04 0.082 0 0 0 0 0.0008 631.4 0.06
11 0.007 0.14 0.35 0.012 0.0008 0 11.91 6.81 2.94 0.020 0.0065 0 0 0 0 0 0 0 0 644.0 0.04
Comparative steel 12 0.008 0.14 0.46 0.013 0.0010 0.02 11.84 7.21 2.91 0.025 0.0061 0.002 0.06 0.084 0 0.0006 0 0 0 587.2 0.63
13 0.007 0.20 0.45 0.010 0.0010 0.02 11.96 6.93 2.89 0.028 0.0051 0 0.06 0.089 0 0 0 0 0 595.3 0.12
14 0.016 0.17 0.71 0.015 0.0010 0.03 11.80 7.20 2.92 0.030 0.0055 0.004 0.06 0.001 0 0 0 0 0 580.3 0.98
15 0.013 0.22 0.44 0.011 0.0010 0.02 12.65 6.12 3.08 0.026 0.0050 0 0.06 0.088 0 0 0 0 0 683.3 -1.32
16 0.013 0.15 0.71 0.012 0.0009 0.26 11.83 6.54 2.92 0.022 0.0053 0.002 0.06 0.079 0 0 0 0 0 629.7 0.34
F1＝922.6-554.5C-50.9Mn+2944.8P+1.056Cr-81.1Ni+95.8Mo-l25.1Ti-1584.9Al-376.1NF2＝30C+0.5Mn+Ni+0.5Cu-1.5Si-Cr-Mo+7.9
Melting has the steel of the chemical ingredients shown in the table 1.As shown in table 1, the chemical ingredients of sample 1～sample 11 is all in the scope of chemical ingredients of the present invention.
At this, the left side that makes formula (1) is that the left side of F1, formula (2) is F2, obtains the F1 and the F2 of each sample.At this moment, for the sample that does not contain Ti, make the coefficient of " Ti " in the F1 be " 0 "; For the sample that does not contain Cu, make the coefficient of " Cu " in the F2 be " 0 ".
The F1 of sample 1～sample 11 and F2 are all within the scope of the invention.Specifically, F1 is more than 600, and F2 is more than 0.
On the other hand, in sample 12 and sample 13, though chemical ingredients within the scope of the invention, the value of F1 is less than 600.In sample 14～sample 16, C content has surpassed higher limit of the present invention.And the F1 value of sample 14 is less than 600, and the F2 value of sample 15 is less than 0.
Sample 1～sample 16 molten steel are cast and made the continuous casting part.The continuous casting part that produces is carried out forge hot and hot rolling and make the steel plate of a plurality of thick 15mm, wide 120mm, long 1000mm.With the steel plate air cooling after forge hot and the hot rolling to normal temperature.Implement following test with the gained steel plate.
1. tempering range
At first, a plurality of steel plates that obtain are quenched.At this moment, quenching temperature is 910 ℃.Then, the steel plate after quenching is implemented tempering.At this moment, tempering temperature is changed in 450～650 ℃ temperature range.Being used in each tempering temperature has implemented the steel plate of temper and has carried out tension test.Specifically, producing the parallel portion diameter by steel plate is that 6.35mm, parallel portion length are the pole sample of 25.4mm.The pole sample that use is made is implemented tension test based on JIS Z2241 at normal temperature, has obtained yielding stress.After the tension test, the yielding stress of having obtained each sample is the tempering range Δ T in 758～860MPa scope.In addition, with yield strength 0.2% as yielding stress.
The yielding stress that each sample has been shown in the table 2 is the tempering range of 758～860MPa.
Table 2
Sequence number ΔT(℃)
Steel of the present invention 1 110
2 80
3 100
4 110
5 45
6 80
7 50
8 55
9 40
10 110
11 100
Comparative steel 12 10
13 10
14 20
15 25
16 20
Δ T in the table 2 is that the yielding stress of each sample is the top temperature in the tempering temperature of 758～860MPa and the difference of minimum temperature.Wherein unit is ℃.
As shown in table 2, the Δ T of sample 1～sample 11 is more than 40 ℃.On the other hand, sample 12 and sample 13 since the F1 value less than 600, so Δ T is less than 40 ℃.Sample 14 because C content is higher and the F1 value less than 600, so Δ T is less than 40 ℃.Sample 15 and sample 16 are because C content is higher, so Δ T is less than 40 ℃.
What Fig. 2 represented is the tempering temperature of sample 1 and sample 14 and the relation between the yielding stress.As shown in Figure 2, the F1 value is that the obliquity of tempering curve C1 in the yielding stress scope of 758～860MPa of the sample 1 more than 600 is less, and tempering range Δ T1 is 110 ℃.And the F1 value is bigger less than the obliquity of 600 the tempering curve C2 of sample 14 in the yielding stress scope of 758～860MPa, and tempering range Δ T2 is decreased to 20 ℃.
2. toughness
The result of the toughness value of each sample of trying to achieve has been shown in the table 3.
Table 3
Sequence number F2 Yielding stress (MPa) Absorption energy (J) in the time of-40 ℃
Steel of the present invention 1 0.20 804.0 185
2 0.25 782.0 182
3 0.14 812.0 176
4 0.24 805.0 185
5 0.03 813.0 188
6 0.26 838.0 187
7 0.18 854.0 192
8 0.30 808.0 190
9 0.06 841.0 188
10 0.06 807.0 190
11 0.04 773.0 194
Comparative steel 12 0.63 848.0 160
13 0.12 815.0 165
14 0.98 851.0 167
15 -1.32 844.0 81
16 0.34 841.0 171
Toughness test is carried out in accordance with the following methods.The gained steel plate is quenched at 910 ℃, implement temper then, so that yielding stress reaches the value shown in the table 3.The steel plate after the temper is implemented in use, produces the wide V-shaped groove sample based on the 10mm of JIS Z2202.
The V-shaped groove sample that use is made is implemented Charpy impact test based on JIS Z2242-40 ℃ temperature, has obtained the absorption energy.
Endergonic unit in the table 3 is J.Because sample 1～sample 11 all is that the F2 value is more than 0, surpass 100J so absorb energy, demonstrated high tenacity.And sample 15 since its F2 value less than 0, so the absorption energy is low.
3. erosion resistance
Erosion resistance under moistening carbon dioxide environment is to test by following carbon dioxide corrosion to estimate.Implemented to carry out the sample that steel that quenching and tempering handles has cut out wide 20mm * thick 3mm * long 50mm when estimating under the identical condition with toughness.After with No. 60 sand paper the surface of the sample that cuts out being ground, again the specimen surface after this grinding is carried out degreasing and drying.
The sample of making was flooded 720 hours in 25% the NaCl aqueous solution, and this NaCl aqueous solution is the CO that makes 9.73 air pressure 2H with 0.014 air pressure 2S is saturated to form.In addition, in the test with the temperature maintenance of the aqueous solution at 165 ℃.
After the test, obtained the corrosion reduction of sample.Specifically, the value that deducts the sample weight gained after the test the sample weight before test is the corrosion reduction.And by confirming that with watching specimen surface has or not local corrosion.If it is higher that the corrosion reduction, then can be judged as the erosion resistance of this sample under moistening carbon dioxide environment less than 7.7g and do not produce local corrosion.
Then, by carrying out following SSC test the anti-SSC under moistening hydrogen-sulfide environmental is estimated.When estimating under the identical condition with toughness, with having implemented that quenching and tempering is handled and the steel plate diameter of having produced parallel portion be that 6.3mm, parallel portion length are the tension specimen of 25.4mm.The tension specimen that use is made carries out endurance test (proof ring test) based on NACE TM0177-96 Method A.At this moment, sample was flooded 720 hours in 20% the NaCl aqueous solution, this NaCl aqueous solution is the H that makes 0.03atm 2S (CO 2Bal.) saturated and.The pH of the NaCl aqueous solution is 4.5, in the test with the temperature maintenance of the aqueous solution at 25 ℃.The test back is by having flawless with affirmation soon.
The result of corrosion resistance test has been shown in the table 4.
Table 4
Sequence number The carbon dioxide corrosion test The SSC test
1 ○ ○
2 ○ ○
3 ○ ○
4 ○ ○
5 ○ ○
6 ○ ○
7 ○ ○
8 ○ ○
9 ○ ○
10 ○ ○
11 ○ ○
" zero " in the carbon dioxide corrosion test in the table, expression corrosion reduction is less than 7.7g and do not produce local corrosion.And " zero " in SSC corrosion test expression does not crack.Sample 1～sample 11 all has high corrosion resistance.
Embodiments of the present invention more than have been described, but above-mentioned embodiment only is used to implement example of the present invention.So, the invention is not restricted to above-mentioned embodiment, in the scope that does not break away from its aim, can carry out appropriate variations and implement the present invention above-mentioned embodiment.
The industry utilizability
Martensitic stainless steel of the present invention can be as employed steel in the corrosive environment that contains the corrosive substances such as hydrogen sulfide, carbon dioxide, chlorion. Particularly can be used for the steel pipe that uses with steel, oil well pipe with steel, carbon dioxide eliminating equipment with steel, geothermal power generating device as at the production equipment of the such moistening hydrogen-sulfide environmental of oil well, gas well and moistening carbon dioxide environment.

Claims (5)

1. martensitic stainless steel, in quality %, this martensitic stainless steel contains C:0.001～0.01%, below the Si:0.5%, Mn:0.1～3.0%, below the P:0.04%, below the S:0.01%, Cr:10～15%, Ni:4～8%, Mo:2.8～5.0%, Al:0.001～0.10%, below the N:0.07%, Ti:0～0.25%, V:0～0.25%, Nb:0～0.25%, Zr:0～0.25%, Cu:0～1.0%, Ca:0～0.005%, Mg:0～0.005%, La:0～0.005%, Ce:0～0.005%, all the other compositions are made of Fe and impurity, satisfy following formula (1) and formula (2), have the yielding stress of 758～860MPa;
922.6-554.5C-50.9Mn+2944.8P+1.056Cr-81.1Ni+95.8Mo-125.1Ti-1584.9Al-376.1N≥600(1)
30C+0.5Mn+Ni+0.5Cu-1.5Si-Cr-Mo+7.9≥0(2)
At this, the coefficient in the formula is the content (quality %) of each element.
2. martensitic stainless steel according to claim 1 is characterized in that,
Contain more than one elements in Ti:0.005～0.25%, V:0.005～0.25%, Nb:0.005～0.25%, Zr:0.005～0.25%.
3. martensitic stainless steel according to claim 1 is characterized in that,
Contain Cu:0.05～1.0%.
4. martensitic stainless steel according to claim 2 is characterized in that,
Contain Cu:0.05～1.0%.
5. according to each described martensitic stainless steel in the claim 1～4, it is characterized in that,
Contain more than one elements in Ca:0.0002～0.005%, Mg:0.0002～0.005%, La:0.0002～0.005%, Ce:0.0002～0.005%.
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