CN101151388A - Ferritic heat-resistant steel - Google Patents
Ferritic heat-resistant steel Download PDFInfo
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- CN101151388A CN101151388A CNA200680010223XA CN200680010223A CN101151388A CN 101151388 A CN101151388 A CN 101151388A CN A200680010223X A CNA200680010223X A CN A200680010223XA CN 200680010223 A CN200680010223 A CN 200680010223A CN 101151388 A CN101151388 A CN 101151388A
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- 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
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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- 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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- 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
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- 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
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
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Abstract
Disclosed is a heat-resistant steel which is excellent in high-temperature long-term creep strength and creep-fatigue strength. Specifically disclosed is a heat-resistant steel having a composition consisting of, in mass%, 0.01-0.13% of C, 0.15-0.50% of Si, 0.2-0.5% of Mn, not more than 0.02% of P, not more than 0.005% of S, more than 8.0% but less than 12.0% of Cr, 0.1-1.5% of Mo, 1.0-3.0% of W, 0.1-0.5% of V, 0.02-0.10% of Nb, not more than 0.015% of sol. Al, 0.005-0.070% of N, 0.005-0.050% of Nd, 0.002-0.015% of B, and the balance of Fe and impurities. As some of the impurities, less than 0.3% of Ni, less than 0.3% of Co and less than 0.1% of Cu are contained in the heat-resistant steel. This ferritic heat-resistant steel contains Nd inclusions at a density of not less than 10,000 inclusions/mm<3>. This steel may further contain one or more elements selected from Ta, Hf, Ti, Ca and Mg in addition to the above-described components.
Description
Technical field
The present invention relates to a kind of ferrite heat resistant steel.Say in further detail, relate to the ferrite heat resistant steel of long-time creep strength of a kind of high temperature and creep fatigue good strength.High temperature steel of the present invention is applicable to that the heat exchange used at boiler, nuclear energy power generation equipment and chemical industry equipment etc. is with steel pipe, steel heavy plate for pressure vessels, turbine material etc. under high temperature, hyperbaric environment.
Background technology
For the high temperature steel that boiler, nuclear energy power generation equipment and chemical industry equipment etc. use in high temperature, hyperbaric environment, general requirement high temperature creep strength, creep fatigue intensity, erosion resistance and scale resistance etc.
Intensity and the erosion resistance of high Cr ferritic steel in 500～650 ℃ of temperature is better than low alloy steel.In addition, high Cr ferritic steel is characterised in that, because thermal conductivity height and coefficient of thermal expansion are low, therefore, compares heat-resistant anti-fatigue characteristic good and low price with austenitic stainless steel.In addition, have the generation of being difficult to oxide skin and peel off, can not produce a plurality of advantages such as stress corrosion cracking.
From the nineties in the latter half eighties 20th century to 20th century, ASME P91 steel obtains practical application as high-strength ferritic class high temperature steel, uses in the supercritical pressure boiler of vapor temperature more than 566 ℃.In addition, in recent years, the ASME P92 steel that has improved creep strength obtains practical application, and the vapor temperature of using this steel is that the special supercritical pressure boiler about 600 ℃ is applied.
Now, in order to protect environment, need to reduce CO
2Quantity discharged.Therefore, even in thermal power generation boiler, also need higher High Temperature High Pressure.For the ASME P92 steel that makes present practicality also can be in the higher temperature zone, for example about 630 ℃ use down, must use the thicker member of wall thickness.
Because steam power plant will start continually and stop, therefore, especially for the heavy wall member, creep fatigue intensity becomes important.ASME P92 steel is compared with the ASMEP91 steel, and creep strength increases substantially, but creep fatigue intensity is identical.In order to make the more high-temperature high-pressure boiler practicability of High Temperature High Pressure, must improve the creep fatigue intensity of ASMEP92 steel.
Patent documentation 1 and 2 discloses the invention of the high temperature steel that contains 8～14%Cr.In addition, patent documentation 3 discloses the invention of the high temperature steel that contains 8～13%Cr.But the disclosed invention of above-mentioned document will not improve the creep fatigue intensity of high temperature steel as purpose.Though the steel of foregoing invention also can contain Nd, not the following steel that has made full use of the useful effect of Nd inclusion.
Patent documentation 1: TOHKEMY 2001-192781 communique
Patent documentation 2: TOHKEMY 2002-224798 communique
Patent documentation 3: TOHKEMY 2002-235154 communique
Summary of the invention
The object of the present invention is to provide the ferrite heat resistant steel that the long-time creep strength of a kind of high temperature is good and creep fatigue intensity is also good.
Fig. 1 is the figure of an example of the strain waveform of expression creep fatigue test.Fig. 1 (a) expression be a kind of PP waveform, be a kind of to apply strain at a high speed so that the side that stretches does not produce the waveform of creep strain with compression one side.What Fig. 1 (b) represented is a kind of CP waveform.This CP waveform is in order to import the tensile creep strain, and stretch a side with low speed, in compression one side to apply the strained waveform at a high speed.
Life-span under the more above-mentioned PP waveform and the life-span under the CP waveform, the side's life-span that then is subjected under the CP waveform of creep impairment is short.Generally speaking, in 0.4～1.5% full range of strain, carry out creep fatigue test, the high temperature steel life-span of using in the high temperature and high pressure environment of boiler, nuclear energy power generation equipment and chemical industry equipment is estimated.
Because use equipment such as above-mentioned boiler for a long time under High Temperature High Pressure, therefore, each member produces creep strain, bears the load of CP type.In addition, usually in order to ensure the creep fatigue life-span of the member that under High Temperature High Pressure, uses, adopt in actual use to reduce to produce the strained structure.Therefore, for the high Cr ferritic steel that in aforesaid device, uses, need be under the CP waveform, guarantee the creep fatigue life-span in about 0.5% the full range of strain, wherein, this full range of strain of about 0.5% is the full range of strain of above-mentioned creep fatigue test, i.e. low strain zone in 0.4～1.5%.
Above-mentioned ASME P91 and P92 steel 100,000 hours creep strengths in 600 ℃ are respectively about 98MPa and 128MPa, the intensity height of P92 steel.But as can be seen, in 600 ℃, when implementing the creep fatigue test of 0.5% full range of strain in the CP of Fig. 1 waveform, the life-span all is about 3000 circulations, does not have big difference.That is, can draw following result: compare with the P91 steel, though the increase of P92 steel creep strength,, creep fatigue intensity does not improve.Can study some reasons that P92 steel creep fatigue intensity does not improve from this result, in other words, then forgive the reason that creep fatigue intensity reduces.Therefore, the inventor has carried out wholwe-hearted research for P92 steel creep fatigue intensity is improved.
At first, for owing to thinking that creep fatigue intensity does not have the influence of the micro-delta ferrite that the alloying element segregation of the reason that improves causes to carry out the research of following (a).
(a) influence of investigation delta ferrite
The P92 steel also contains amount of ferrite forming element (Mo, W, Nb, V etc.) except containing the composition that the 9Cr ferrite heat resistant steel was contained in the past.Therefore, may be in crystal boundary portion the delta ferrite of remaining denier.In order to remove delta ferrite fully, prepare to make the P92 steel to contain the starting material of micro Cu, Ni or Co (these are austenite former), relatively creep fatigue intensity respectively.Test temperature is made as 600 ℃, full range of strain is made as 0.5%.Consequently, the life-span is about 1600～2100 circulations, compares with the P92 steel, can assert the trend with reduction.
From The above results as can be seen, the reason that the creep fatigue intensity of P92 steel does not have to improve is not a delta ferrite, but if contain superfluous austenite former, then creep fatigue intensity reduces.
Then, for of the effect of clear and definite crystal boundary, carry out the investigation of following (b) to the generation of creep fatigue intensity.
(b) original austenite size of particles is to the investigation of the influence of P92 steel creep fatigue intensity
Normalizing temperature is made as 1050 ℃ and 1200 ℃, handles the P92 steel, make original austenite size of particles become about 25 μ m and 125 μ m.Then, by tempering carry out modified, tensile strength is become after about 710MPa, carry out the creep fatigue test.Test temperature is made as 600 ℃, full range of strain is made as 0.5%.
Above-mentioned test-results is, common is life-span under the 25 μ m states to be approximately 3000 circulations at particle diameter, and relative therewith, particle diameter is to be about 2300 circulations in the life-span of the coarse-grained steel of 125 μ m.From above-mentioned situation as can be seen, even coarse-grained steel intensity is identical with fine grained steel, the creep fatigue life-span also can reduce.
(c) the high reason of creep fatigue intensity of analysis fine grained steel
The high reason of creep fatigue intensity for the fine grained steel of seeing from above-mentioned (b) test-results is investigated.
We can say that generally for the creep properties in the high temperature, the creep properties that trends towards coarse-grained steel is good.Here, the creep strength of the sample that uses of investigation (b) test in 600 ℃, 160MPa.Consequently, the rupture time of the sample of 25 μ m size of particles is about 6000 hours, and is relative therewith, and the rupture time of the sample of 125 μ m size of particles is about 9000 hours, as described in the past, and the creep strength height of coarse-grained steel.The raising of the creep fatigue intensity of fine grained steel can't be described by tensile strength and creep strength from this result as can be seen.
Increase the grain boundary area of fine grained steel.Think if grain boundary area increases, then suppress the segregation of impurity element, especially S such as P, S, As, Sn.Therefore, investigate to the segregation of crystal boundary for S.
Usually, ferrite heat resistant steel contains about 0.001% S as impurity.In actual product, be difficult to S is reduced to degree less than 0.001%.Even in the laboratory, make, can not avoid sneaking into S from alloying element, therefore, be difficult in the general melting method, eliminate segregation by reducing S.
Generally, in the phenomenon that the segregation owing to S etc. causes, temper brittleness is well-known.As everyone knows, produce temper brittleness in certain the certain temperature scope about 600 ℃, when martensite is carried out tempering, but micro-Mo can effectively reduce this temper brittleness.
If the creep fatigue phenomenon is relevant with the segregation of S, consider then what Mo content and creep fatigue characteristic have related.At this, investigation Mo content becomes 0.01%, 0.07%, 0.13%, 0.33% and 1.83% o'clock creep fatigue intensity (test temperature is that 600 ℃, full range of strain are 0.5%).Consequently, Mo content is 0.13% and 0.33% o'clock, and the life-span is about 3000 circulations, and during Mo content little (0.01% and 0.07%), the life-span is about about 2000 circulations, creep fatigue intensity reduces.From above-mentioned situation as can be seen, Mo plays certain beneficial effect for creep fatigue intensity.But, can confirm that as if increasing Mo content again, being at 1.83% o'clock, then the creep fatigue life-span becomes about 2500 circulations, fatigue characteristic have the trend of reduction on the contrary.
Then, the existence of S in steel investigated.Its result as shown in Figure 2, as can be seen, S exists with the form of MnS.When implementing the creep fatigue test in high temperature, the S that enters as MnS becomes free, and to grain boundary segregation, then this S produces bad influence to the creep fatigue characteristic.
(d) fixing S
As mentioned above, the segregation that becomes free S produces bad influence to the creep fatigue characteristic, then except Mn, also contains more firmly and S bonded element, thereby may improve creep fatigue intensity.
Therefore, for the Ca that may form sulfide, Mg, Nd, La and Ce the influence that creep fatigue intensity produces is studied.
Consequently, as can be seen, when containing 0.025%Nd, except MnS, the Nd inclusion is S fixedly.This Nd inclusion is meant " oxide compound of Nd " and " oxide compound of Nd and the complex inclusion of sulfide "." oxide compound of Nd and the complex inclusion of sulfide " can be described as directly fixedly S.On the other hand, " oxide compound of Nd " is also by S segregation and indirect securement S around it.Fig. 3 represents an example as the Nd inclusion, observed in containing the steel of Nd " complex inclusion of Nd oxide compound and sulfide ".
As mentioned above, as can be seen, above-mentioned condition, promptly in 600 ℃ of test temperatures and the 0.5% full range of strain to containing directly and the steel of the Nd of indirect securement S when carrying out the creep fatigue test, be about 7000 circulations fatigue lifetime, has tremendously and improve.
In addition, as can be seen, the creep fatigue life-span (experimental temperature is 600 ℃, range of strain is 0.5% entirely) of containing the steel of Ca, Mg, La and Ce respectively separately is about 3000～4000 circulations, the creep fatigue life-span of containing the steel of mentioned component and N d simultaneously is 6000～7000 circulations, and the creep fatigue life-span has tremendously improves.
(e) compound interpolation Nd and Cu, Ni or Co
As described in above-mentioned (a), as can be seen, contain micro-austenite former, promptly the creep fatigue intensity of the steel of Cu, Ni or Co has the trend of reduction.For further clear and definite this phenomenon, estimate for the creep fatigue life-span of the steel that in containing the steel of micro-Nd, has added micro Cu or Ni or Co.
Its result shows, the creep fatigue life-span of containing the steel of Nd and micro Cu, Ni or Co simultaneously is approximately 4000 circulations, compares with the steel that does not contain Nd, and then creep fatigue characteristic improves, but compare with the steel that contains Nd separately, then the creep fatigue life-span reduces significantly.
Can obtain the conclusion of following (1)～(4) from above-mentioned research.
Mo more than (1) 0.1% helps to improve the creep fatigue characteristic.
(2) though most of S is fixed as MnS, in the pyritous fatigue test, a part of S becomes unbound state, to grain boundary segregation, and creep fatigue intensity is reduced.
(3) make steel contain Nd, the oxide compound by Nd or fix S as the composite impurities of oxide compound and sulfide a part of S is fixed as MnS, thereby creep fatigue intensity is improved significantly.10000/mm of density at the Nd inclusion
3Its effect is remarkable when above.And " Nd inclusion " is the general name of above-mentioned " oxide compound of Nd " and " oxide compound of Nd and the complex inclusion of sulfide ".
(4) Cu, Ni and the Co as austenite former reduces creep fatigue intensity.Can confirm also have this trend even contain the steel of micro-Nd.Can think that the reason that produces above-mentioned phenomenon is that Cu, Ni and Co promotion are fixed to the phenomenon of S formation unbound state in the creep fatigue test of MnS.
The present invention who makes based on above-mentioned result of study is a purport with following high temperature steel.Below, the % relevant with component content represents quality %.
(1) a kind of ferrite heat resistant steel, contain 0.01～0.13% C, 0.15～0.50% Si, 0.2～0.5% Mn, P below 0.02%, S below 0.005%, greater than 8.0% and less than 12.0% Cr, 0.1～1.5% Mo, 1.0～3.0% W, 0.1～0.5% V, 0.02～0.10% Nb, sol.Al below 0.015%, 0.005～0.070% N, 0.005～0.050% Nd, 0.002～0.015% B, remainder is formed by Fe and impurity, Ni in the impurity is less than 0.3%, Co is less than 0.3%, Cu is less than 0.1%, also contain the Nd inclusion, the density of this Nd inclusion is 10000/mm
3More than.
(2) according to above-mentioned (1) described ferrite heat resistant steel, it is characterized in that, replace a part of Fe, contain the element more than a kind among the Ti below Ta, the Hf below 0.04% and 0.04% below 0.04%.
(3) according to above-mentioned (1) or (2) described ferrite heat resistant steel, it is characterized in that, replace a part of Fe, contain a kind or 2 kinds of elements among the Mg below the Ca and 0.005% below 0.005%.
(4) according to any described ferrite heat resistant steel in above-mentioned (1)～(3), it is characterized in that except Nd, the total amount of rare earth element is below 0.04% in the impurity.
(5) according to any described ferrite heat resistant steel in above-mentioned (1)～(4), it is characterized in that, be 0.01%/sec in the side strain speed that stretches, be 0.8%/sec in compression one side strain speed, full range of strain is under 0.5% the condition, the creep fatigue life-span under 600 ℃ the CP waveform 5000 be time circulate more than.
Description of drawings
Fig. 1 is the figure of an example of the strain waveform of expression creep fatigue test.
Fig. 2 is the figure that is illustrated in observed sulfide in the ASME P92 steel.
Fig. 3 is the figure that is illustrated in observed in the steel that contains Nd " oxide compound of Nd and the complex inclusion of sulfide ".
Embodiment
1. chemical constitution
At first, the action effect of the composition that constitutes high temperature steel of the present invention and the reason of limited content are described.
C：0.01～0.13％
C is as the austenite stable element, the tissue of stabilized steel.In addition, form MC carbide or M (C, N) carbonitride, help to improve creep strength.M among MC and the M (C, N) is an alloying element.But the C less than 0.01% can not fully obtain above-mentioned effect, and the delta ferrite amount increases intensity is reduced sometimes.On the other hand, if C content surpasses 0.13%, then not only processibility, weldability variation, and, cause that carbide begins the alligatoring of condensing from the use initial stage, can cause long-time creep strength to reduce.Therefore, C content need be restricted to below 0.13%.The upper limit that is more preferably and lower limit are respectively 0.08% and 0.11%.
Si：0.15～0.50％
Si in addition, also is to be used to improve the necessary element of water-fast vapor-phase oxidation performance as the deoxidant element of steel and be contained in the steel.With lower limit set is not damage 0.15% of water-fast vapor-phase oxidation performance.On the other hand, if Si content surpasses 0.50%, then creep strength significantly reduces, and therefore, the upper limit is set at 0.50%.Particularly in the occasion of paying attention to water-fast vapor-phase oxidation, preferably the lower limit set with the Si amount is 0.25%.
Mn：0.2～0.5％
Mn works as deoxidant element and austenite stable element.In addition, form MnS and fix S.In order to obtain above-mentioned effect, need contain the Mn more than 0.2%.On the other hand, if surpass 0.5%, then cause creep strength to reduce.Therefore, the proper content of Mn is 0.2～0.5%.In addition, be limited to 0.3% under more preferred.
Below the P:0.02%, below the S:0.005%
Because reductions such as the hot workability that makes steel as the P and the S of impurity, weldability, creep strength, creep fatigue intensity, therefore, content is low more good more.But, because significant steel purification can cause cost to increase substantially, therefore, the high limit of tolerance of P is set at 0.02%, the high limit of tolerance of S is set at 0.005%.
Cr: greater than 8.0% and less than 12.0%
Cr is used for guaranteeing the indispensable element of steel of the present invention in the erosion resistance of high temperature, scale resistance, especially water-fast vapor-phase oxidation characteristic.In addition, Cr forms carbide, improves creep strength.In order to obtain above-mentioned effect, need make its content surpass 8.0%.But, if the content of Cr is too much, then cause long-time creep strength to reduce, therefore, this content is made as less than 12.0%.What be more preferably is limited to 8.5% down, in addition, is more preferably and is limited to less than 10.0%.
Mo：0.1～1.5％
Mo helps to improve creep strength as the solution strengthening element.And the result that the mutual relationship of Mo content and creep fatigue intensity is studied in great detail shows that Mo can play the effect that improves the creep fatigue characteristic more than 0.1%, if content surpasses 1.5%, then causes long-time creep strength to reduce.Therefore, Mo content is 0.1～1.5%, and is suitable.The lower limit that is more preferably and the upper limit are respectively 0.3% and 0.5%.
W：1.0～3.0％
W helps to improve creep strength as the solution strengthening element.And a part of W is solid-solubilized in the Cr carbide, suppresses the condensing of carbide, alligatoring, helps to improve creep strength.But, content less than 1.0% situation under, above-mentioned effect is little.On the other hand,, then promote to generate delta ferrite, cause creep strength to reduce if Mo content surpasses 3.0%.Therefore, the preferable range of W content is 1.0～3.0%.Following being limited to that is more preferably surpasses 1.5% amount, in addition, is more preferably and is limited to 2.0%.
V：0.1～0.5％
V utilizes the solution strengthening effect, forms other trickle carbonitrides, helps to improve creep strength.In order to bring into play this effect, its content need be made as more than 0.1%.On the other hand,, then promote to generate delta ferrite, cause creep strength to reduce, therefore, the upper limit should be set at 0.5% if V content surpasses 0.5%.The lower limit that is more preferably and the upper limit are respectively 0.15% and 0.25%.
Nb：0.02～0.10％
Nb forms trickle carbonitride, helps to improve long-time creep strength.In order to bring into play this effect, need contain the Nb more than 0.02%.But, if this content is too much, then promote the generation of delta ferrite, cause long-time creep strength to reduce.Therefore, the preferred content of Nb is 0.02～0.10%.The lower limit that is more preferably and the upper limit are respectively 0.04% and 0.08%.
Below the Al:0.015%
Al uses as the reductor of molten steel, if its content surpasses 0.015%, then causes creep strength to reduce, and therefore, the upper limit should be controlled to be below 0.015%.Be limited to 0.010% on being more preferably.
N：0.005～0.070％
N is identical with C, effective as the austenite stable element.In addition, N separates out nitride or carbonitride, increases the hot strength of steel.In order to bring into play this effect, need contain the N more than 0.005%.On the other hand,, then not only when melting, produce bubble, cause producing welding flaw, and because the alligatoring of nitride and carbonitride causes creep strength to reduce if N content is too much.Therefore, the upper limit of N content should be set at 0.070%.The following of the N content that is more preferably is limited to 0.020%.
Nd：0.005～0.050％
As mentioned above, Nd increases substantially creep fatigue intensity.In order to bring into play this effect, need contain the Nd more than 0.005%.But, if surpass 0.050%, then form thick nitride, cause creep strength to reduce, therefore, the upper limit should be set at 0.050%.The upper content limit that is more preferably is 0.040%.
B：0.002～0.015％
B plays the vital role that strengthens hardenability, guarantees hot strength.This effect is 0.002% obvious when above at B content, if content surpasses 0.015%, then reduces weldability and long-time creep strength.
Ni: less than 0.3%, Co: less than 0.3%, Cu: less than 0.1%
As mentioned above, even above-mentioned austenite stable element content is very little, also can reduce creep fatigue intensity.But, can sneak into micro-Ni, Co and Cu from the melting raw material inevitably sometimes.Therefore, the present invention is controlled to be Ni and Co less than 0.3% respectively, and Cu is controlled to be less than 0.1%.If it is in above-mentioned scope, then less to the bad influence of creep fatigue intensity generation.
The 1st forms branch: Ta, Hf and Ti
Mentioned component is for adding the composition more than a kind or 2 kinds as required.Proper content separately when adding is as described below.
Below the Ta:0.04%, below the Hf:0.04%, below the Ti:0.04%
Help to improve creep strength owing to Ta, Hf and Ti form trickle carbonitride, therefore, contain these compositions as required.In order to give full play to this effect, preferably contain more than 0.005% respectively.But, even content surpasses 0.04% respectively,, this effect closes because reaching full, can reduce creep strength on the contrary.Therefore, preferably respectively the upper limit of its content is set at 0.04%.
The 2nd forms branch: Ca and Mg
Mentioned component is for adding the composition of a kind or 2 kinds as required.Proper content when adding is as described below respectively.
Below the Ca:0.005%, below the Mg:0.005%
These two kinds of elements all improve the hot workability of steel.Therefore, especially when hope improves the hot-work of steel, can contain wherein any one separately or compoundly contain two kinds.Because respectively 0.0005% its effect when above is remarkable at content, therefore, preferably the lower limit with content is set at 0.0005% respectively.But if the content of every kind of element all surpasses 0.005%, then creep strength reduces, and therefore, the upper limit should be set at 0.005%.
Rare earth element except Nd: below 0.04%
When adding Nd, rare earth elements such as La, Ce are sneaked into as impurity sometimes.But, if the ree content except Nd amounts to below 0.04%, then can not produce big influence to characteristics such as creep strength, creep ductilities, therefore, allow and contain 0.04% at most.
2.Nd inclusion
One of feature of steel of the present invention is that the density of Nd inclusion is 10000/mm
3More than.
As mentioned above, observed Nd inclusion is " oxide compound of Nd " and " oxide compound of Nd and the composite impurities of sulfide " in steel of the present invention.Specifically, be Nd
2O
3, Nd
2O
2S
4, Nd
2O
2SO
4, Nd
2O
2S etc.
The diameter of Nd inclusion is approximately about 0.3 μ m～1 μ m, has nothing in common with each other, and observes the Nd inclusion usually in containing the steel of micro-Nd.But in the steel that contains a large amount of Co, Ni and Cu, it is many that MnS becomes, and the Nd inclusion significantly reduces.And, if the density of Nd inclusion is less than 10000/mm
3, can't confirm that then creep fatigue intensity improves.Therefore, the density of Nd inclusion is necessary for 10000/mm
3More than.
3. manufacture method
Can make steel of the present invention by industrial normally used producing apparatus.That is, obtain the steel of the chemical constitution of the present invention regulation, can purify by stoves such as electric furnace, converters, deoxidation and adjust composition by adding alloying element.Especially be adjusted to timesharing in the needs strictness, also can be before adding alloying element, adopt molten steel is implemented the method that vacuum-treat etc. is suitably handled.
With 10000/mm
3The method that above Nd inclusion imports in the steel is as described below.That is, from refining the pig iron to the stage of steel-making, carry out abundant deoxidation in advance with C, Si, Mn, Al etc.This be because, if molten steel in oxygen level many, the yield rate variation of then adding Nd.Afterwards, when implementing ingot casting method, before the founding steel ingot, adjust Nd composition in addition, will carry out adding Nd before the founding, thereby generate the Nd inclusion.In addition, when implementing Continuous casting process, before molten steel is imported tundish, adjust Nd composition in addition, afterwards, Nd is added in the tundish, thereby, the Nd inclusion generated.By only Nd being done last adjustment, can generate the Nd inclusion of appropriate amount.In addition, plate slab, steel billet or the steel ingot that is cast is processed into steel pipe or steel plate etc.
When making weldless steel tube, for example, push steel billet and tubulation, or be rolled tubulation, also can pass through the big hammer welded pipe of Ai Shi washing pipe tubulation manufactured diameter with inclination roller-type roll piercing mill.When making steel pipe, can implement cold working as required, adjust size.After the steel pipe of making is carried out appropriate heat treatment, as required, implement surface treatments such as shot peening, pickling.
As steel plate, hot-rolled steel sheet and cold-rolled steel sheet are arranged.By hot rolling slab, can obtain hot-rolled steel sheet, if cold rolling this hot-rolled steel sheet then can obtain cold-rolled steel sheet.
Embodiment
The steel that uses the vacuum induction melting furnace melting to have the chemical constitution shown in the table 1, forming diameter is the 50kg steel ingot of 144mm.Code A～M represents steel of the present invention, code 1～22 expression comparative steel.To code be the steel of A～M and code be 15～20 steel after carrying out abundant deoxidation with C, Si, Mn and Al, will add Nd before the founding.From beginning during melting, to code is 21 steel, add Nd; For code is that 22 steel only carries out implementing to add Nd to it after the deoxidation by carbon (C).
Above-mentioned steel ingot is carried out forge hot, hot rolling, form the thick plate of 20mm.Then, after in 1050 ℃ of temperature, keeping 1 hour, carry out air cooling (AC).In 760 ℃～780 ℃, kept 3 hours again, carry out the temper of air cooling (AC).Choose sample from above-mentioned plate, the length direction that makes sample is a rolling direction, carries out the distribution investigation of repture test, creep fatigue test and Nd inclusion in following condition.
(1) repture test
Sample: diameter 6.0mm, the metering punctuate between apart from 30mm, 600 ℃ of test temperatures, load stress 160Mpa,
Test subject: rupture time (h).
(2) creep fatigue test
Sample: diameter 10mm, the metering punctuate between apart from 25mm, 600 ℃ of test temperatures (in the atmosphere)
Strain waveform: CP waveform, full range of strain Δ ε
t=0.5%
Rate of straining: the side that stretches is that 0.01%/sec, compression one side are 0.8%/sec
Test subject: creep fatigue life-span N
f(inferior circulation)
(3) distribution of Nd inclusion investigation
When carrying out hot-work, from starting material, cut sample, after grinding, corroding, make the refinement replica by the C evaporation, when carrying out 2000 times of amplification observations with electron microscope, analyze (energy dispersive x ray analysis) by EDX and carry out the evaluation of impurity, determine that the number of Nd inclusion is (individual/mm
2) quantity, on duty 3/2 with this, to separate out density (individual/mm thereby be converted into
3).And, observe with 10 times of visual fields, with its mean value as separating out density.
The distribution investigation result of repture test result, creep fatigue test-results and the Nd inclusion of table 2 expression steel of the present invention and comparative steel.
Table 1
Table 1
Table 2
| Code | Creep fracture time (hr) | The creep fatigue life-span (circulation) | The Nd inclusion is (individual/mm 3) | Remarks |
| A | 7092 | 6955 | 127476 | |
| B | 6280 | 5660 | 51941 | |
| C | 7806 | 7624 | 50444 | |
| D | 6661 | 5428 | 79161 | |
| E | 7745 | 5747 | 139727 | |
| F | 6840 | 5254 | 78571 | |
| G | 7831 | 6127 | 113590 | |
| H | 7006 | 6747 | 69146 | |
| I | 6399 | 6977 | 109778 | |
| J | 6279 | 5946 | 49007 | |
| K | 6715 | 6635 | 58781 | |
| L | 6904 | 5158 | 86908 | |
| M | 7259 | 5260 | 135225 | |
| 1 | 2115 | 3189 | 0 | ASME P91 is suitable |
| 2 | 6243 | 2960 | 0 | ASME P92 is suitable |
| 3 | 5542 | 2077 | 0 | |
| 4 | 4986 | 1625 | 0 | |
| 5 | 6915 | 1857 | 0 | |
| 6 | 6587 | 2927 | 0 | ASME P92 is suitable |
| 7 | 6156 | 1809 | 0 | |
| 8 | 7146 | 2131 | 0 | |
| 9 | 6445 | 2490 | 0 | |
| 10 | 7674 | 3464 | 0 | |
| 11 | 6120 | 3338 | 0 | |
| 12 | 6721 | 3504 | 0 | |
| 13 | 7620 | 2777 | 0 | |
| 14 | 6869 | 3945 | 1453 | |
| 15 | 3799 | 5440 | 330107 | |
| 16 | 6088 | 4071 | 131446 | |
| 17 | 6505 | 3913 | 123897 | |
| 18 | 6465 | 4035 | 195277 | |
| 19 | 7107 | 4392 | 85205 | |
| 20 | 7354 | 4054 | 159896 | |
| 21 | 6593 | 3629 | 4840 | |
| 22 | 7538 | 2957 | 6982 |
As shown in table 2, be that 1 ASME P91 steel is compared with code, the creep fracture time that code is 2, code is 6 ASME P92 steel is long, and creep strength is obviously high.But the creep fatigue life-span is roughly the same.That is, do not see the obvious improvement in creep fatigue life-span from ASME P92 steel.
The code that contains micro Cu, Ni or Co is that the creep strength of 3～5 steel and code are that 2 steel is in par, but the creep fatigue life-span is obviously low.
For at code being Mo produces creep-rupture strength and creep fatigue intensity in 2,6,7,8 and 9 the steel influence when investigating, with code be 2 and code be that 6 steel is compared, the less code of Mo content be 7 with code be that the creep fatigue intensity of 8 steel is low.In addition, the more code of Mo content is that the creep fatigue intensity of 9 steel is also low.
The code that contains micro-La, Ce, Ca or Mg is that the creep strength of 10～13 steel and creep fatigue intensity are that 2 steel is in par with code all, does not confirm characteristic and improves.
On the other hand, satisfy the steel creep fracture time of code A～code M of prescribed condition of the present invention and code and be 2 steel and be in par, but the creep fatigue life-span significantly improves.
The code that Nd content is lower than specialized range of the present invention is that the creep fatigue improved strength of 14 steel is insufficient.On the other hand, the code that contains superfluous Nd is that the creep strength of 15 steel is low.
The code that contains micro-Nd and austenite former Cu, Ni or Co is that the creep strength of 16～18 steel and code are that 2 steel is in par, and creep fatigue intensity and code are that 2 steel has been compared some improvement.But, be that the steel of A～M is compared with the code that does not contain Cu, Ni or Co or reduce mentioned component content, then creep fatigue intensity is obviously low.
The Nd that contains in specialized range of the present invention, the Mo code that exceeds specialized range of the present invention be 19 and code be that 20 steel is compared with the steel that does not contain Nd, the creep fatigue life-span is long.But, be that the steel of A～M is compared with the code of Mo content in specialized range of the present invention, creep fatigue intensity is obviously low.
Code be 21 and code be the chemical constitution of 22 steel in specialized range of the present invention, the distribution density of Nd inclusion does not reach specialized range of the present invention.Above-mentioned steel just adds Nd owing to fully do not carry out deoxidation, therefore, forms very thick Nd oxide compound, and the density of Nd inclusion significantly reduces, and the creep fatigue life-span is in low-level.
Application possibility on the industry
Steel of the present invention be under 600～650 ℃ of high temperature, heat resisting steel that long-time creep strength and creep fatigue intensity are high. This steel is brought into play splendid effect with steel pipe, steel heavy plate for pressure vessels, turbine with material as the heat exchange of using in fields such as thermal power generation, nuclear energy power generation or chemical industry, and is industrially very useful.
Claims (5)
1. ferrite heat resistant steel, contain quality % and be 0.01～0.13% C, 0.15～0.50% Si, 0.2～0.5% Mn, P below 0.02%, S below 0.005%, greater than 8.0% and less than 12.0% Cr, 0.1～1.5% Mo, 1.0～3.0% W, 0.1～0.5% V, 0.02～0.10% Nb, so1.Al below 0.015%, 0.005～0.070% N, 0.005～0.050% Nd, 0.002～0.015% B, remainder is made of Fe and impurity, Ni in the impurity is less than 0.3%, Co is less than 0.3%, Cu is less than 0.1%, contain the Nd inclusion, the density of this Nd inclusion is 10000/mm
3More than.
2. ferrite heat resistant steel according to claim 1 is characterized in that, replaces a part of Fe, contains in element more than a kind among the Ta of quality % below 0.04%, Hf below 0.04% and the 0.04% following Ti.
3. ferrite heat resistant steel according to claim 1 and 2 is characterized in that, replaces a part of Fe, contains in a kind or 2 kinds of elements among the Mg below the Ca and 0.005% of quality % below 0.005%.
4. according to any described ferrite heat resistant steel in the claim 1～3, it is characterized in that except Nd, the total amount of rare earth element is below 0.04% in the impurity.
5. according to any described ferrite heat resistant steel in the claim 1～4, it is characterized in that, in the side strain speed of stretching is that 0.01%/sec, compression one side strain speed are 0.8%/sec, full range of strain is under 0.5% the condition, more than 5000 circulations of creep fatigue life-span under 600 ℃ the CP waveform.
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|---|---|---|---|
| JP111149/2005 | 2005-04-07 | ||
| JP2005111149 | 2005-04-07 |
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|---|---|
| US (1) | US20080112837A1 (en) |
| EP (1) | EP1867745B1 (en) |
| JP (1) | JP4609491B2 (en) |
| KR (1) | KR100933114B1 (en) |
| CN (1) | CN100580119C (en) |
| CA (1) | CA2603772A1 (en) |
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| WO (1) | WO2006109664A1 (en) |
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- 2006-04-06 JP JP2007512941A patent/JP4609491B2/en not_active Expired - Fee Related
- 2006-04-06 CA CA002603772A patent/CA2603772A1/en not_active Abandoned
- 2006-04-06 CN CN200680010223A patent/CN100580119C/en not_active Expired - Fee Related
- 2006-04-06 KR KR1020077021398A patent/KR100933114B1/en active IP Right Grant
- 2006-04-06 WO PCT/JP2006/307315 patent/WO2006109664A1/en active Application Filing
- 2006-04-06 EP EP06731263.7A patent/EP1867745B1/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20070103081A (en) | 2007-10-22 |
| EP1867745A4 (en) | 2011-08-24 |
| EP1867745A1 (en) | 2007-12-19 |
| WO2006109664A1 (en) | 2006-10-19 |
| EP1867745B1 (en) | 2014-08-06 |
| CA2603772A1 (en) | 2006-10-19 |
| JPWO2006109664A1 (en) | 2008-11-13 |
| CN100580119C (en) | 2010-01-13 |
| KR100933114B1 (en) | 2009-12-21 |
| US20080112837A1 (en) | 2008-05-15 |
| JP4609491B2 (en) | 2011-01-12 |
| DK1867745T3 (en) | 2014-08-25 |
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