WO2000003050A1 - ACIER FERRITIQUE THERMORESISTANT A TENEUR ELEVEE EN Cr - Google Patents

ACIER FERRITIQUE THERMORESISTANT A TENEUR ELEVEE EN Cr Download PDF

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Publication number
WO2000003050A1
WO2000003050A1 PCT/JP1999/003231 JP9903231W WO0003050A1 WO 2000003050 A1 WO2000003050 A1 WO 2000003050A1 JP 9903231 W JP9903231 W JP 9903231W WO 0003050 A1 WO0003050 A1 WO 0003050A1
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WO
WIPO (PCT)
Prior art keywords
steel
less
toughness
present
content
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP1999/003231
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English (en)
Japanese (ja)
Inventor
Atsushi Sawaragi
Hiroyuki Sennba
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Corp
Original Assignee
Sumitomo Metal Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Metal Industries Ltd filed Critical Sumitomo Metal Industries Ltd
Priority to EP99925355A priority Critical patent/EP1103626B1/fr
Priority to DE69904336T priority patent/DE69904336T2/de
Publication of WO2000003050A1 publication Critical patent/WO2000003050A1/fr
Priority to US09/754,050 priority patent/US20020020473A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C22C38/002—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
    • C22C38/18—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
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/30—Ferrous alloys, e.g. steel alloys containing chromium with cobalt
    • 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
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • 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
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips

Definitions

  • the present invention relates to high Cr heat-resistant steel, and more particularly, to a heat exchange steel pipe, a steel plate for a pressure vessel, and a turbine used in a high-temperature and high-pressure environment such as a boiler, a nuclear power plant, and a chemical industrial facility.
  • a heat exchange steel pipe a steel plate for a pressure vessel
  • a turbine used in a high-temperature and high-pressure environment such as a boiler, a nuclear power plant, and a chemical industrial facility.
  • Heat-resistant steel used in high-temperature, high-pressure environments such as poilers, nuclear power plants, and chemical industry facilities generally requires high-temperature strength, corrosion resistance, oxidation resistance, toughness, and the like.
  • boiler steam conditions are being increased in temperature and pressure. That is, under supercritical pressure conditions From 538 ° C and 246 atm, operation in the ultra-supercritical condition of 625 ° C and above and 300 atm and above is planned in the future. With such changes in steam conditions, the required performance of steel pipes for boilers and the like is becoming increasingly severe. For this reason, conventional high Cr ferritic steels have not been able to sufficiently respond to the long-term cleave strength at high temperatures as described above.
  • Austenitic stainless steel is capable of meeting the severe conditions described above, but is expensive. For this reason, attempts have been made to improve the characteristics of high-Cr steels, which are cheaper than austenitic stainless steels.
  • the present inventors have developed an inexpensive high Cr frit heat-resistant steel excellent in cleave strength and toughness even after a long period of time under high-temperature, high-pressure ultra-supercritical pressure conditions (Japanese Patent Laid-Open No. 8-85850). JP-A-9-71845, JP-A-71-71846).
  • An object of the present invention is to provide a high Cr ferrite heat-resistant steel which is extremely excellent in high-temperature long-term cleave strength and toughness which can be used under high-temperature and high-pressure steam of 625 ° C or more and 300 atm or more.
  • the gist of the present invention relating to the high Cr ferritic heat-resistant steel is as follows.
  • T a 0.01 to 0.15%
  • Nb 0.01 to 0.15%
  • Nd 0.001 to 0.2%
  • N less than 0.02%
  • a high Cr heat-resistant steel that has high content of Nd and N and satisfies the following formula, and the balance is Fe and unavoidable impurities.
  • the present inventors have studied in detail the effect of each element on the high-temperature long-time creep properties and toughness of the previously developed high Cr ferritic heat-resistant steel containing Nd in order to further improve the properties. As a result, the following findings were obtained and the present invention was completed.
  • Nd has the effect of fixing oxygen in steel as Nd oxide and suppressing some of Nb and V as precipitation strengthening elements that precipitate fine carbides that contribute to creep strength from becoming oxides. is there. Also, Nd has an action of generating carbides such as Nd C 2 . These carbides precipitate finely and stably even after a long time at a high temperature, which contributes to the improvement of the high-temperature long-time creep strength.
  • C forms MC (M is an alloying element) type carbide, that is, M 7 C 3 and M 23 C 6 type carbides.
  • M is an alloying element
  • This carbide contributes to the improvement of the creep strength and stabilizes the structure as C itself as an austenite stabilizing element. If it is less than 0.02%, the precipitation of carbides is insufficient, and the amount of ⁇ ferrite is increased, so that sufficient creep strength and toughness cannot be obtained. However, if it is contained in a large amount exceeding 0.15%, agglomeration and coarsening of carbides will occur from the initial stage of use, and consequently long-term creep strength will decrease, and workability and weldability will also deteriorate, so the upper limit is set.
  • ⁇ is effective as an element that fixes deoxidation and S, and also contributes as an austenite stabilizing element. To obtain these effects, 0.05% or more is necessary, but if it exceeds 1.5%, the toughness deteriorates. % To 1.5%. Preferably it is 0.05-0.7%.
  • Impurities P and S are desirably low from the viewpoints of hot workability, weldability and toughness, but directly affect the properties of the steel of the present invention up to 0.03% and 0.015%, respectively. Therefore, the upper limits were set at 0.03% and 0.015%, respectively.
  • Cr is an element indispensable for securing the corrosion resistance and oxidation resistance at high temperatures of the steel of the present invention, particularly the steam oxidation resistance. It also forms carbides to improve creep strength. In addition, it has a function of forming a dense oxide film mainly composed of Cr to improve corrosion resistance and oxidation resistance. To obtain these effects, the content needs to be 8% or more. However, when contained in large amounts, the formation of ⁇ -ferrite is promoted and the toughness is degraded, so the upper limit was set to 13%. Preferably it is 9 to 12%.
  • W is one of the main strengthening elements of the steel of the present invention.
  • W is finely dispersed and precipitated as an intermetallic compound such as Fe 7 W 6 type phase or Fe 2 W type Laves phase during high temperature use, and contributes to improvement of long-term creep strength.
  • it also forms part of a solid solution in Cr carbide and suppresses agglomeration and coarsening of carbide and contributes to maintaining and maintaining strength.
  • the content was set to 1.5% to 4%. Preferably it is 2-3.5%.
  • Co is an austenite stabilizing element and is an essential element in the steel of the present invention to which W is positively added.
  • C unlike Ni, which is the same austenitic stabilizing element, has the effect of improving creep strength without reducing creep strength. To achieve these effects The addition of more than 2% is necessary, but if it exceeds 6%, the A c 1 transformation point of the steel decreases significantly and conversely, the creep strength decreases. Preferably it is 2-4%.
  • V is an important element in the steel of the present invention and forms fine carbonitrides, thereby contributing to improvement in creep strength.
  • the content In order to exhibit the effect, the content must be 0.1% or more. Even if the content exceeds 0.5%, the effect is saturated. Therefore, the content is set to 0.1% to 0.5%. Preferably it is 0.15 to 0.35%.
  • Ta and Nb are elements that form fine carbonitrides and contribute to the improvement of creep strength.
  • 0.01% or more is required for each.However, if the content exceeds 0.15%, the effect saturates, so 0.011% to 0.15% And Preferably it is 0.01 to 0.1%.
  • Nd is a carbide such as Nd C 2 largely contributes to the suppression of recovery softening of the martensite structure since the precipitates finely and stable at high temperature for a long time side, greatly improve the creep strength.
  • it is necessary to contain 0.001% or more.However, if the content exceeds 0.2%, the toughness is deteriorated, so that 0.001% to 0.2%. did.
  • it is 0.005 to 0.15%.
  • N is effective as an austenite stabilizing element, like C, but in steels containing Nd, as the N content increases, coarse NdN remains as inclusions in the steel, thus improving creep strength. Is not fully exhibited, and the toughness also deteriorates. Therefore, in order to fully exert the effect of N d Therefore, the upper limit of N content in steel must be less than 0.02%. When importance is placed on toughness, it is desirable to adjust the balance between Nd and N content within a range that satisfies the following equation. Nd (%) ⁇ 5 xN (%) + 0.10 (%)
  • B has the effect of Ru finely dispersed precipitation of the M 23 C 6 type carbide when added trace, high temperature for a long time contributes to the improvement of creep characteristics.
  • the quenchability is enhanced and also plays an important role in ensuring high-temperature strength. The effect becomes remarkable at 0.0005% or more.
  • the content exceeds 0.02%, coarse precipitates are formed and the toughness is deteriorated. Therefore, the B content was set to 0.0005 to 0.02%. Preferably, it is 0.002 to 0.01%.
  • A1 must be 0.001% or more as a deoxidizer for molten steel. On the other hand, 0
  • the creep strength is lowered, so the content was made 0.001 to 0.05%.
  • the content is 0.001 to 0.03%.
  • Si is used as a deoxidizer for molten steel as necessary. Si is effective for improving the steam oxidation resistance at high temperatures, but when contained in a large amount exceeding 1%, the toughness is degraded. Therefore, Si is set to 0 to 1% in the present invention. In particular, when importance is attached to steam oxidation resistance, the Si content is preferably set to 0.1% or more.
  • Mo is an element to be contained as necessary and contributes to the improvement of creep strength as a solid solution strengthening element. Intermetallic compounds precipitate. In Mo-containing steels, such intermetallic compounds do not contribute to the improvement of creep strength because they precipitate very coarsely, and also reduce the toughness after aging. Therefore, the content of Mo was set to 0 to 1%.
  • C a is 0 to 0.02%, others are 0 to 0.2%
  • One or more of Ca, La, Ce, Y and Hf are contained as necessary. These elements, even in very small amounts, strengthen the grain boundaries to improve the cleave strength and also contribute to the improvement of hot workability. However, if added excessively, the hot workability deteriorates. Therefore, the upper limit of these elements was set to 0.02% for Ca and 0.2% for La, Ce, Y and Hf.
  • inventive steel I to Q comparative steel
  • Tables 3 and 4 show the clip rupture time and the Charpy impact value (JZcm 2 ) measured in these tests.
  • Table 3 (Example of the present invention)
  • Table 4 (Comparative example) Kirara Kimore 650 C x98MPa Wildness + Kibo Symbol Symphony Fiber & recitation. +
  • the cleave rupture times of the symbols 1, 2, and 3 steels and the steels of 4, 5, and 6 of the steels of the present invention in which the N content is less than 0.02% are within the ranges specified by the present invention for the N content of each comparative steel. It can be seen that it is clearly improved compared to the steel A and the steel B, which exceed The effect of improving the cleave rupture life by reducing N is also evident in the comparison between the steels 7 to 17 of the steel of the present invention and the comparative steels C to M.
  • the symbols N, O, P, and Q of the comparative steels are those where the contents of Nd and N do not satisfy the following formula. In this case, there is almost no difference in creep rupture life as compared with the symbols 17, 19, 21, and 23 of the present invention that satisfy the following expression, but the impact value is lower. Therefore, when importance is placed on toughness, it is desirable to adjust the Nd and N contents within a range that satisfies the following equation.
  • the high Cr heat resistant steel of the present invention is excellent in high-temperature long-time cleave strength and toughness at room temperature at a high temperature of 625 ° C or more, and is used for heat exchange in fields such as nuclear power generation and the chemical industry. It has excellent effects when used as a steel pipe, pressure vessel steel plate, and turbine material, and is 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 ferritique thermorésistant Cr contenant 0,02 % à 0,15 % de C, 0,05 % à 1,5 % de Mn, 0,03 % ou moins de P, 0,015 % ou moins de S, 8 % à 13 % de Cr, 1,5 % à 4 % de W, 2 % à 6 % de Co, 0,1 % à 0,5 % de V, 0,01 % à 0,15 % de Ta, 0,01 % à 0,15 % de Nb, 0,001 % à 0,2 % de Nd, moins de 0,02 % de N, 0,0005 % à 0,02 % de B, 0,001 % à 0,05 % de Al, à la condition que les teneurs en Nb et N satisfassent la formule indiquée, lequel présente une excellente résistance au fluage sous condition de température élevée sur une longue durée et une excellente dureté, il peut être utilisé dans des conditions de pression supercritique extrême à 650 °C ou davantage et sous 300 atm.
PCT/JP1999/003231 1998-07-08 1999-06-16 ACIER FERRITIQUE THERMORESISTANT A TENEUR ELEVEE EN Cr Ceased WO2000003050A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP99925355A EP1103626B1 (fr) 1998-07-08 1999-06-16 ACIER FERRITIQUE THERMORESISTANT A TENEUR ELEVEE EN Cr
DE69904336T DE69904336T2 (de) 1998-07-08 1999-06-16 Hochchromhaltiger, wärmebeständiger, feritischer stahl
US09/754,050 US20020020473A1 (en) 1998-07-08 2001-01-05 Heat resistant high chromium ferritic steel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10/193084 1998-07-08
JP19308498A JP3982069B2 (ja) 1998-07-08 1998-07-08 高Ｃｒフェライト系耐熱鋼

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US09/754,050 Continuation US20020020473A1 (en) 1998-07-08 2001-01-05 Heat resistant high chromium ferritic steel

Publications (1)

Publication Number Publication Date
WO2000003050A1 true WO2000003050A1 (fr) 2000-01-20

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Country Link
US (1) US20020020473A1 (fr)
EP (1) EP1103626B1 (fr)
JP (1) JP3982069B2 (fr)
DE (1) DE69904336T2 (fr)
WO (1) WO2000003050A1 (fr)

Families Citing this family (18)

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Publication number Priority date Publication date Assignee Title
US6696016B1 (en) * 1999-09-24 2004-02-24 Japan As Represented By Director General Of National Research Institute For Metals High-chromium containing ferrite based heat resistant steel
KR100708616B1 (ko) * 2000-08-19 2007-04-18 두산중공업 주식회사 원자력 발전소, 고속증식로, 핵융합로의 고온 및고압부위에 사용되는 저방사화 고크롬 페라이트계내열합금
JP2002146484A (ja) * 2000-11-10 2002-05-22 Sanyo Special Steel Co Ltd 高強度フェライト系耐熱鋼
JP4614547B2 (ja) * 2001-01-31 2011-01-19 独立行政法人物質・材料研究機構 高温クリープ破断強度及び延性に優れたマルテンサイト系耐熱合金とその製造方法
CA2603772A1 (fr) * 2005-04-07 2006-10-19 Sumitomo Metal Industries, Ltd. Acier ferritique resistant a la chaleur
US20070087250A1 (en) * 2005-10-13 2007-04-19 Lewis Daniel J Alloy for fuel cell interconnect
DE102005061790A1 (de) * 2005-12-23 2007-07-05 Mtu Aero Engines Gmbh Werkstoff für Bauteile einer Gasturbine
RU2308532C1 (ru) * 2006-03-20 2007-10-20 Юлия Алексеевна Щепочкина Сталь
RU2333287C2 (ru) * 2006-09-26 2008-09-10 Открытое Акционерное Общество "Научно-Производственное Объединение "Центральный Научно-Исследовательский Институт Технологии Машиностроения", Оао "Нпо Цниитмаш" Жаропрочная сталь
RU2335569C2 (ru) * 2006-09-26 2008-10-10 Открытое Акционерное Общество "Научно-Производственное Объединение "Центральный Научно-Исследовательский Институт Технологии Машиностроения", Оао "Нпо Цниитмаш" Сталь
CN101743336B (zh) * 2007-03-29 2011-12-14 阿尔斯托姆科技有限公司 抗蠕变钢
EP2157202B1 (fr) * 2007-06-04 2017-07-12 Nippon Steel & Sumitomo Metal Corporation Acier ferrite résistant à la chaleur
EA017766B1 (ru) * 2008-03-11 2013-03-29 Государственное Научное Учреждение "Физико-Технический Институт Национальной Академии Наук Беларуси" Жаростойкая литейная сталь
CN104907470B (zh) * 2015-04-27 2017-01-11 上海宏钢电站设备铸锻有限公司 13Cr9Mo2Co1NiVNbNB钢锻件的制造方法
JP6575392B2 (ja) * 2015-05-19 2019-09-18 日本製鉄株式会社 高Ｃｒフェライト系耐熱鋼
CN108754335B (zh) * 2018-08-22 2019-09-10 武汉钢铁有限公司 一种屈服强度≥550MPa的焊接结构用耐火耐候钢及生产方法
JP7502041B2 (ja) * 2019-02-21 2024-06-18 株式会社神戸製鋼所 高Ｃｒフェライト系耐熱鋼用溶接材料
JP7136325B2 (ja) * 2019-03-19 2022-09-13 日本製鉄株式会社 フェライト系耐熱鋼

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JPH07331389A (ja) * 1994-06-03 1995-12-19 Kawasaki Steel Corp 製造性、加工性および高温長時間時効後の高温強度に優れた自動車排気マニホールド用ステンレス鋼
JPH0885849A (ja) * 1994-09-20 1996-04-02 Sumitomo Metal Ind Ltd 高Ｃｒフェライト系耐熱鋼
JPH0885850A (ja) * 1994-09-20 1996-04-02 Sumitomo Metal Ind Ltd 高Ｃｒフェライト系耐熱鋼
JPH0971845A (ja) * 1995-09-04 1997-03-18 Sumitomo Metal Ind Ltd 高Ｃｒフェライト系耐熱鋼
JPH0971846A (ja) * 1995-09-05 1997-03-18 Sumitomo Metal Ind Ltd 高Ｃｒフェライト系耐熱鋼

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Title
See also references of EP1103626A4 *

Also Published As

Publication number Publication date
JP2000026940A (ja) 2000-01-25
EP1103626A4 (fr) 2002-01-16
DE69904336T2 (de) 2003-08-21
DE69904336D1 (de) 2003-01-16
US20020020473A1 (en) 2002-02-21
EP1103626A1 (fr) 2001-05-30
EP1103626B1 (fr) 2002-12-04
JP3982069B2 (ja) 2007-09-26

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