WO2006109664A1 - Acier ferritique resistant a la chaleur - Google Patents

Acier ferritique resistant a la chaleur Download PDF

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Publication number
WO2006109664A1
WO2006109664A1 PCT/JP2006/307315 JP2006307315W WO2006109664A1 WO 2006109664 A1 WO2006109664 A1 WO 2006109664A1 JP 2006307315 W JP2006307315 W JP 2006307315W WO 2006109664 A1 WO2006109664 A1 WO 2006109664A1
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Prior art keywords
less
steel
creep
strength
resistant steel
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PCT/JP2006/307315
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English (en)
Japanese (ja)
Inventor
Mitsuru Yoshizawa
Masaaki Igarashi
Mitsuo Miyahara
Yasutaka Noguchi
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Sumitomo Metal Industries, Ltd.
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Application filed by Sumitomo Metal Industries, Ltd. filed Critical Sumitomo Metal Industries, Ltd.
Priority to JP2007512941A priority Critical patent/JP4609491B2/ja
Priority to CA002603772A priority patent/CA2603772A1/fr
Priority to KR1020077021398A priority patent/KR100933114B1/ko
Priority to EP06731263.7A priority patent/EP1867745B1/fr
Priority to DK06731263.7T priority patent/DK1867745T3/da
Publication of WO2006109664A1 publication Critical patent/WO2006109664A1/fr
Priority to US11/905,877 priority patent/US20080112837A1/en

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Classifications

    • 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
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • 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
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • 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

Definitions

  • the present invention relates to a ferritic heat resistant steel. More specifically, it relates to a ferritic heat resistant steel having excellent high-temperature long-term creep strength and creep fatigue strength.
  • the heat-resistant steel of the present invention is suitable for heat exchange steel pipes, pressure vessel steel sheets, turbine materials, and the like used under high temperature and high pressure environments such as boilers, nuclear power generation facilities, and chemical industrial facilities.
  • High temperature creep strength, creep fatigue strength, corrosion resistance, oxidation resistance, and the like are generally required for heat resistant steels used in high temperature and high pressure environments such as boilers, nuclear power generation facilities, and chemical industrial facilities.
  • High Cr ferritic steel is superior to low alloy steel in terms of strength and corrosion resistance at a temperature of 500 to 650 ° C.
  • high Cr fluorescent steel is characterized by excellent thermal fatigue resistance and low cost compared to austenitic stainless steel because of its high thermal conductivity and low coefficient of thermal expansion.
  • ASME P 91 steel was put to practical use as a high-strength ferritic heat-resistant steel and used in supercritical pressure boilers with a steam temperature of 566 ° C or higher.
  • ASME P92 steel with increased creep strength has been put into practical use, and an ultra-supercritical boiler with a steam temperature of about 600 ° C has been put into practical use.
  • Patent Documents 1 and 2 disclose inventions of heat-resisting steels containing 8 to 14% Cr.
  • Patent Document 3 discloses an invention of a heat resistant steel containing 8 to 13% Cr.
  • the inventions disclosed in these documents have not been made for the purpose of improving the creep fatigue strength of heat-resistant steel.
  • the steels of these inventions are not steels that utilize the effective action of Nd inclusions described later.
  • Patent Document 1 JP 2001-192781 A
  • Patent Document 2 JP 2002-224798 A
  • Patent Document 3 Japanese Patent Laid-Open No. 2002-235154
  • An object of the present invention is to provide a ferritic heat resistant steel that is excellent in high-temperature long-term creep strength and excellent in creep fatigue strength.
  • FIG. 1 is a diagram showing an example of a strain waveform in a creep fatigue test.
  • A in the figure shows the PP waveform, which is a waveform that applies strain at high speed so that creep strain does not occur on both the tension side and the compression side.
  • B shows the CP waveform. This is a waveform that loads the strain with the tensile side at a low speed and the compression side at a high speed to introduce tensile creep strain.
  • the lifetime under the PP waveform is compared with the lifetime under the CP waveform, the lifetime is shorter in the CP waveform that undergoes creep damage.
  • the life of heat-resistant steel used in high-temperature and high-pressure environments in boilers, nuclear power generation facilities, and chemical industrial facilities is evaluated by conducting creep fatigue tests in the entire strain range of 0.4 to 1.5%.
  • each member Since the equipment such as the boiler is used for a long time under high temperature and pressure, each member is subjected to creep strain and receives a CP-type load. In general, the actual machine is constructed to reduce the generated strain in order to ensure the creep fatigue life of members used under high temperature and pressure. Therefore, the high Cr ferritic steels used in these facilities are It is necessary to ensure the creep fatigue life in the total strain range of the creep fatigue test, that is, the total strain of about 0.5%, which is the low strain region of 0.4 to 1.5%.
  • the ASME P91 and P92 steels have a 100,000 hour creep strength at 600 ° C. of about 98 MPa and 128 MPa, respectively, and the P92 steel has higher strength.
  • the CP waveform shown in Fig. 1 has a total strain range of 0.5. / 0 was subjected to a creep fatigue test, life revealed no approximately 3000 cycles much different either.
  • the creep strength of P92 steel was higher than that of P91 steel, the creep fatigue strength was not improved. From these results, it is considered that P92 steel contains some cause for the creep fatigue strength not improving, in other words, the cause for the decrease in creep fatigue strength. Therefore, the present inventors conducted extensive studies to improve the creep fatigue strength of P92 steel.
  • ⁇ 92 steel is rich in ferrite-forming elements (Mo, W, Nb, V, etc.). Therefore, a very small amount of ⁇ ferrite may remain at the grain boundary.
  • materials with a small amount of Cu, N and Co (these are austenite forming elements) were prepared in ⁇ 92 steel, and the creep fatigue strength was compared.
  • the test temperature was 600 ° C and the total strain range was 0.5%. As a result, the life was about 1600-2100 cycles, which was a tendency to decrease compared to P92 steel.
  • ferritic heat resistant steel contains about 0.001% of S as an impurity. At the actual product level, it is difficult to reduce S to a level lower than 0.001%. Even in laboratory production, it is difficult to eliminate segregation by reducing S in the usual melting method because S is unavoidable from alloying elements.
  • temper embrittlement is known as a phenomenon caused by segregation such as S. Tempering brittleness occurs when martensite is tempered in a certain temperature range of around 600 ° C. It is known that trace amounts of Mo are effective in reducing this.
  • the Mo content is 0.01%, 0.07%, 0.13
  • the creep fatigue strength (test temperature is 600 ° C and the total strain range is 0.5%) when the ratio was changed to%, 0.33%, and 1.83% was investigated.
  • the Mo content was 0.13% and 0.33%, the life was about 3000 cycles.
  • the Mo content was small (0.01% and 0.07%), the creep fatigue strength was about 2000 cycles. Decreased. From this, it became clear that Mo has made a certain contribution to the taper fatigue strength.
  • the Mo content was further increased to 1.83%, the creep fatigue life was about 2500 cycles, and the fatigue characteristics tended to decrease rather.
  • Nd inclusions fix S in addition to MnS.
  • the Nd inclusion means “Nd oxide” and “composite inclusion of Nd oxide and sulfide”. “Nd oxide and sulfide complex inclusions” fix S directly. On the other hand, “Nd oxide” also indirectly fixes S by segregating S around it.
  • Fig. 3 shows "composite inclusions of Nd oxide and sulfide" observed in Nd-containing steel.
  • the creep fatigue life (test temperature is 600 ° C, total strain range 0.5%) of steel containing Ca, Mg ⁇ La and Ce alone is a force of about 3000 to 4000 cycles. It was revealed that the steel containing the component together with Nd has a life of 6000 to 7000 cycles, and the creep fatigue life is dramatically improved.
  • the creep fatigue life of steel containing a small amount of Cu, N or Co along with Nd is about 4000 cycles, and the creep fatigue properties are improved compared to steel containing no Nd.
  • the creep fatigue life was found to be significantly inferior to that of the steel containing Nd alone.
  • Nd inclusion is a general term for the above “Nd oxide” and “combined inclusion of Nd oxide and sulfide”.
  • Nb 0.02 to 0.10%
  • sol.Al 0.015% or less
  • Nd 0.005 to 0.050%
  • B 0.002 to 0.015%
  • Fe and impurities Ferrite with Ni power of less than 0.3% of impurities
  • Co of less than 0.3%
  • Cu of less than 0.1%
  • the density of the Nd inclusions is 10000 / mm 3 or more Heat resistant steel.
  • FIG. 1 is a diagram showing an example of a strain waveform in a creep fatigue test.
  • FIG. 2 is a diagram showing sulfides observed in ASME P92 steel.
  • FIG. 3 is a view showing “composite inclusions of Nd oxide and sulfide” observed in Nd-containing steel.
  • C stabilizes the structure of steel as an austenite stabilizing element.
  • MC carbide or M (C, N) carbonitride is formed, contributing to the improvement of creep strength.
  • M in MC and M (C, N) is an alloying element.
  • the C content is If it exceeds 0.13%, not only the workability and weldability will deteriorate, but also the agglomeration and coarsening of the carbide will occur from the beginning of use, and the creep strength will be reduced for a long time. Therefore, the C content must be limited to 0.13% or less. More desirable lower and upper limits are 0.08% and 0.11%, respectively.
  • Si is contained as a deoxidizing element in steel and is also an element necessary for improving the steam oxidation resistance.
  • the lower limit is 0.15%, which does not impair the steam oxidation resistance.
  • the upper limit is made 0.50%.
  • the lower limit of Si content is preferably 0.25%.
  • ⁇ contributes as a deoxidizing element and an austenite stabilizing element.
  • MnS is formed and S is fixed. In order to obtain these effects, a content of 0.2% or more is necessary. On the other hand, if it exceeds 0.5%, the creep strength is reduced. Therefore, the appropriate content of Mn is 0.2-0.5%. A more preferred lower limit is 0.3%.
  • Impurities P and S deteriorate the hot workability, weldability, creep strength, and creep fatigue strength of steel, so the lower the content, the better.
  • the upper limit is set to 0.02% for P and 0.005% for S.
  • Cr is an indispensable element for ensuring the corrosion resistance and oxidation resistance at high temperatures of the steel of the present invention, particularly the steam oxidation resistance.
  • Cr forms carbides and improves creep strength.
  • the content power needs to exceed 0.0%.
  • a more preferred lower limit is 8.5%, and a more preferred upper limit is less than 10.0%.
  • Mo contributes to the improvement of creep strength as a solid solution strengthening element. Furthermore, as a result of detailed examination of the correlation between the Mo content and the taper fatigue strength, 0.1% or more of Mo is considered to be the creep fatigue property. It has been found that this contributes to the improvement of the creep strength and that when the content exceeds 1.5%, the creep strength decreases for a long time. Therefore, the appropriate Mo content is 0.1-1.5%. More preferred lower and upper limits are 0.3% and 0.5, respectively. / 0 .
  • W contributes to the improvement of creep strength as a solid solution strengthening element.
  • a part of it dissolves in Cr carbide, which suppresses the agglomeration and coarsening of the carbide and contributes to the creep strength.
  • those effects are small at less than 1.0%.
  • the Mo content strength exceeds ⁇ 3.0%, the formation of ⁇ ferrite is promoted and the creep strength is reduced. Therefore, the appropriate range of W content is 1.0-3.0%.
  • a more preferable lower limit is an amount exceeding 1.5%, and a more preferable upper limit is 2.0%.
  • V contributes to the improvement of creep strength by solid solution strengthening action and by forming fine carbonitrides. In order to exert its effect, its content needs to be 0.1% or more. On the other hand, if the V content force exceeds SO.5%, the formation of ⁇ ferrite is promoted and the creep strength is reduced, so 0.5% should be the upper limit. More preferred lower and upper limits are 0.15% and 0.25%, respectively.
  • Nb contributes to the improvement of creep strength for a long time by forming fine carbonitrides. In order to exert the effect, it is necessary to contain 0.02% or more. However, if the content is too large, the formation of ⁇ ferrite is promoted and the creep strength is lowered for a long time. Therefore, the appropriate content of Nb is 0.02 to 0.10%. More preferred lower and upper limits are 0.04% and 0.08%, respectively.
  • A1 is used as a deoxidizer for molten steel, but if its content exceeds 0.015%, the creep strength decreases, so the upper limit should be kept to 0.015% or less. A more preferred upper limit is 0.010%.
  • N is effective as an austenite stabilizing element.
  • N is nitride or Increases the high temperature strength of the steel by precipitating carbonitrides. 0 to bring out the effect.
  • N content is 0.020%.
  • Nd 0.005 to 0.050%
  • Nd greatly improves the creep fatigue strength. In order to exert the effect, it is necessary to contain 0.005% or more. However, if it exceeds 0.050%, coarse nitrides are formed and the creep strength is lowered, so the upper limit should be 0.050%. More preferred, the upper limit of the content is 0.040%.
  • Ni less than 0.3%
  • Co less than 0.3%
  • Cu less than 0.1%
  • these austenite stabilizing elements lower the creep fatigue strength even with a slight content.
  • trace amounts of Ni, Co, and Cu may be unavoidable from mixing with the melted raw material. Therefore, in the present invention, Ni and Co are suppressed to less than 0.3% and Cu is suppressed to less than 0.1%, respectively. Within the above range, the adverse effect on creep fatigue strength is small.
  • Group 1 ingredients Ta, H «3 ⁇ 4 and Ti
  • Ta 0.04% or less
  • Hf 0.04% or less
  • Ti 0.04% or less
  • Ta, H and Ti are included as necessary because they form fine carbonitrides and contribute to the improvement of creep strength.
  • each content is 0.005% or more.
  • the upper limit of each content is 0.0 4% is recommended.
  • Group 2 ingredients Ca and Mg
  • Rare earth elements such as La and Ce may be mixed as impurities when Nd is added. However, if the total content of rare earth elements excluding Nd is 0.04% or less, there is no significant effect on the properties such as creep strength and creep ductility, so up to 0.04% is allowed.
  • Nd inclusions are contained at a density of 10000 / mm 3 or more.
  • Nd inclusions observed in the steel of the present invention are “Nd oxide” and “Nd oxide and sulfide composite inclusion”. Specifically, Nd 0, Nd 0 S, Nd 0 SO
  • the diameter of the Nd inclusion is about 0.3 ⁇ ! Nl inclusions are usually observed in steels containing a small amount of Nd. However, in steels rich in Co, Ni and Cu, MnS increases and Nd inclusions decrease significantly. And when the density of Nd inclusions is less than 10,000 Zm m 3 , the improvement of creep fatigue strength is not recognized. Therefore, the density of Nd inclusions must be 10000 / mm 3 or more.
  • the steel according to the present invention can be produced by a production facility usually used industrially. . That is, in order to obtain a steel having the chemical composition defined in the present invention, the components may be adjusted by scouring in a furnace such as an electric furnace or converter, and by deoxidation and inclusion of alloy elements. In particular, when strict component adjustment is required, the molten steel should be subjected to an appropriate treatment such as vacuum treatment before adding the alloy elements.
  • a method for introducing 10,000 Nd inclusions of Zmm 3 or more into steel is as follows.
  • Nd inclusions are produced by adjusting the composition other than Nd before pouring into the ingot and adding Nd just before pouring.
  • Nd inclusions are produced by adjusting the composition other than Nd before introducing molten steel to the tundish and then adding Nd to the tundish.
  • a billet is extruded, rolled with an inclined roll-type piercer, or a large-diameter forged pipe is formed by an Ernolt pipe method. Just do it.
  • the dimensions can be adjusted by cold working as necessary.
  • the steel pipe that has been produced is appropriately heat-treated and then subjected to surface treatment such as shot peening and pickling as necessary.
  • the steel sheet there are a hot-rolled steel sheet and a cold-rolled steel sheet.
  • a hot-rolled steel sheet can be obtained by hot rolling a slab, and a cold-rolled steel sheet can be obtained by cold rolling this hot-rolled steel sheet.
  • Test piece Diameter 6.0 mm, distance between gauge points: 30 mm, test temperature: 600 ° C, load stress: 160 MPa, test item: breaking time (h).
  • Test piece Diameter 10 mm, distance between gauge points: 25 mm, test temperature: 600 ° C (in air)
  • Test item Creep fatigue life N (cycle)
  • Table 2 shows the creep rupture test results, creep fatigue test results, and Nd inclusion distribution survey results of the steels of the present invention and the comparative steel.
  • ASME P92 steel with code 2 and code 6 has a clearly higher creep strength with a longer creep rupture time. However, the creep fatigue life is almost the same. That is, ASME P92 steel shows no significant improvement in creep fatigue life.
  • the steels of code 10 to code 13 containing a small amount of La, Ce, Ca or Mg have the same level of tapping strength and creep fatigue strength as the steel of code 2, and the improvement in the properties was recognized. I can't help.
  • the steels from code A to code M that satisfy the conditions specified in the present invention have significantly improved force S and creep fatigue life, which have the same creep rupture time as steel of code 2.
  • the steels of reference numerals 21 and 22 have a chemical composition within the range defined by the present invention, but the distribution density of Nd inclusions does not satisfy the range defined by the present invention. In these, since Nd was added without sufficient deoxidation, a very coarse Nd oxide was formed, the density of Nd inclusions was significantly reduced, and the creep fatigue life was low.
  • the steel of the present invention is a heat-resistant steel excellent in long-term creep strength and creep fatigue strength at a high temperature of 600 to 650 ° C.
  • This steel has excellent effects as a steel tube for heat exchange, steel plates for pressure vessels, and materials for turbines used in fields such as thermal power generation, nuclear power generation and chemical industry. Demonstrate and extremely useful in industry.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

L'invention concerne un acier résistant à la chaleur présentant une excellente résistance à long terme et à haute température au fluage et au fluage combiné à la fatigue. L'invention concerne en particulier un acier résistant à la chaleur, ayant une composition en % massiques consistant en 0,01 à 0,13 % de C, 0,15 à 0,50 % de Si, 0,2 à 0,5 % de Mn, au plus 0,02 % de P, au plus 0,005 % de S, plus de 8,0 % mais moins de 12,0 % de Cr, 0,1 à 1,5 % de Mo, 1,0 à 3,0 % de W, 0,1 à 0,5 % de V, 0,02 à 0,10 % de Nb, au plus 0,015 % de sol. d’Al, 0,005 à 0,070 % de N, 0,005-0,050 % de Nd, 0,002 à 0,015 % de B, le reste étant du Fe et des impuretés. Quelques-unes de ces impuretés contenues dans l'acier résistant à la chaleur sont constituées de moins de 0,3 % de Ni, moins de 0,3 % de Co et moins de 0,1 % de Cu. Cet acier ferritique résistant à la chaleur contient des inclusions Nd avec une densité d’au moins 10 000 inclusions/mm3. En plus des composants décrits précédemment, cet acier peut également contenir un ou plusieurs éléments choisis parmi Ta, Hf, Ti, Ca et Mg.
PCT/JP2006/307315 2005-04-07 2006-04-06 Acier ferritique resistant a la chaleur WO2006109664A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2007512941A JP4609491B2 (ja) 2005-04-07 2006-04-06 フェライト系耐熱鋼
CA002603772A CA2603772A1 (fr) 2005-04-07 2006-04-06 Acier ferritique resistant a la chaleur
KR1020077021398A KR100933114B1 (ko) 2005-04-07 2006-04-06 페라이트계 내열강
EP06731263.7A EP1867745B1 (fr) 2005-04-07 2006-04-06 Acier ferritique resistant a la chaleur
DK06731263.7T DK1867745T3 (da) 2005-04-07 2006-04-06 Ferritisk varmebestandigt stål
US11/905,877 US20080112837A1 (en) 2005-04-07 2007-10-05 Ferritic heat resistant steel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-111149 2005-04-07
JP2005111149 2005-04-07

Related Child Applications (1)

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US11/905,877 Continuation US20080112837A1 (en) 2005-04-07 2007-10-05 Ferritic heat resistant steel

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WO2006109664A1 true WO2006109664A1 (fr) 2006-10-19

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PCT/JP2006/307315 WO2006109664A1 (fr) 2005-04-07 2006-04-06 Acier ferritique resistant a la chaleur

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US (1) US20080112837A1 (fr)
EP (1) EP1867745B1 (fr)
JP (1) JP4609491B2 (fr)
KR (1) KR100933114B1 (fr)
CN (1) CN100580119C (fr)
CA (1) CA2603772A1 (fr)
DK (1) DK1867745T3 (fr)
WO (1) WO2006109664A1 (fr)

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JP2016176120A (ja) * 2015-03-20 2016-10-06 新日鐵住金株式会社 高温クリープ特性に優れた高Ｃｒフェライト系耐熱鋼

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CA3028947A1 (fr) * 2016-06-29 2018-01-04 Nippon Steel & Sumitomo Metal Corporation Acier ferritique resistant a la chaleur et element de transfert thermique ferritique
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