US3826689A - Austenite type heat-resisting steel having high strength at an elevated temperature and the process for producing same - Google Patents

Austenite type heat-resisting steel having high strength at an elevated temperature and the process for producing same Download PDF

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US3826689A
US3826689A US00233255A US23325572A US3826689A US 3826689 A US3826689 A US 3826689A US 00233255 A US00233255 A US 00233255A US 23325572 A US23325572 A US 23325572A US 3826689 A US3826689 A US 3826689A
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steel
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S Ohta
Y Watase
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Kobe Steel Ltd
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Kobe Steel Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese

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  • An austenite type heat-resistant steel containing in Weight percent from 0.1 to 1% carbon, from 0.01 to 3% silicon, from 0.01 to manganese, from 13 to 35% chromium, from 15 to 50% nickel, and the balance essentially impurities and iron, or additionally other elements such as Co, W, Mo, Nb, Ti, Al and/or N, which is characterized by high strength at elevated temperatures, and which is adaptable to forming by forging or centrifugal casting processes, is provided herein.
  • This invention relates to an austenite type heat-resistant steel which is capable of use at elevated temperatures of over about 750 C. This invention further relates to a process for producing the same.
  • Tubes produced by the centrifugal casting process are characterized by high strength at elevated temperatures, but they cannot be formed into small diameter shapes of less than 75 mm. OD. and wall thicknesses of below 6 mm. Moreover, they cannot be formed into tubes of lengths of over 2 m. with diameters of 75 mm. O.D. nor tubes of lengths of over 4 m. with diameters of over 120 mm. O.D. Furthermore, tubes formed by that method have generally inferior inner surfaces and, of course, that technique cannot be used to produce sheets.
  • the ratio of the carbides occupying the grain boundaries should nevertheless be over 30%, preferably over 50%.
  • This steel alloy is produced by a novel process which includes a unique heat treatment technique wherein the steel is heated to a temperature in the range of from 1,l50 C. to the solidus temperature, and it is then cooled to a temperature of 950 C. or higher. Subsequent to this solution heat treatment, after the casting or working of the steel, the slow cooling is followed by water quenching.
  • FIG. 1 is a graphical representation of austenite type stainless steel compositions containing from 0.004 to 1.2% carbon, about 25% chromium and from 8 to 50% nickel;
  • FIG. 2 are photomicrographs of selected composition structures wherein FIGS. I and II are provided for purposes of comparison with structure III of the present invention.
  • FIG. IV shows a structure having a carbide precipitate dispersed within the grains;
  • FIG. 3 is a graphical representation of the ratio of grain boundary occupation of carbide and its effect on creep strength.
  • the present invention provides an austenite type heat resistant steel having high strength properties at elevated temperatures, and containing, in weight percent, from 0.1 to 1% carbon, from 0.01 to 3% silicon, from 0.01 to manganes, from 13 to 35% chromium, from 15 to 50% nickel, and the balance essentially impurities and iron.
  • This alloy is characterized by a precipitation of carbides on the grain boundaries in a continuous or partially-continuous form.
  • the present invention further provides an austenite type heat resistant steel containing, in weight percent, in addition to the alloy elements referred to above, at least one element selected from a group of less than 30% cobalt, less than 10% tungsten, less than 10% molybdenum, less than 5% niobium, less than 5% titanium, less than 5% aluminum and less than 0.5% nitrogen.
  • the present invention presents a process for producing an austenite heat resistant steel having the above-defined composition which is subjected, subsequent to casting or working, to a heat treatment at a temperature of from 1,150 C. up to the solidus temperature, followed by slow cooling from said temperature to a temperature of 950 C. or higher, for a time of from 5 seconds to one hour, and thereafter water quenching.
  • FIG. 2 photomicrographs of austenite type stainless steel structures having a variety of compositions containing from 0.004 to 1.2% carbon, about chromium and from 8 to 50% nickel are shown. Those compositions were subjected to heat at a temperature of 1,280 C. for 10 minutes, slow cooling from 1,280 C. down to 950 C. for one hour, and then water quenching to room temperature.
  • Table I further describes the structures shown in FIG. 2 and indicates the creep rupture strength of the various austenite type compositions.
  • FIG. 2 shows a structure having no carbide precipitate on the grain boundaries; (II) shows carbide precipitate aligned partially on the grain boundaries, with a grain boundary occupying ratio of up to (III) shows a structure having a continuous carbide precipitate on the grain boundaries, and (IV) shows a structure having a carbide precipitate dispersed within the grains.
  • Table I sample No. 101 of the structure (I) where no carbide precipitation occurred on the grain boundaries, comparatively inferior creep rupture strength was obtained.
  • Sample No. 102 of structure (II) carbide was precipitated only in partial alignment with the grain boundaries and likewise showed a comparatively low creep rupture strength.
  • Samples Nos. 102 to 109 of the structure (III) wherein carbide precipitation occurs on the grain boundaries, improved creep rupture strength was obtained.
  • FIG. 3 shows the result of a series of tests made to clarify the efiFect of the quantity ratio of carbide precipitation on the grain boundary on the creep rupture strength of steels containing 0.4% carbon, 25% chromium, and 20% nickel.
  • the amount of Ni can vary from between 15 and 50%.
  • Table 2 shows the creep rupture strength at 1,000 C., of a stainless steel containing about 0.4% carbon, about 45% chromium, and from 8 to 45% nickel. This steel had been subjected to heat treatment at 1,280 C. for 10 minutes, and was then slowly cooled from 1,280 C. down to 950 C. for one hour, followed by rapid cooling to room temperature.
  • Samples 201 and 202 represent structure (I) characterized by a low creep rupture strength, while samples 203 to 208 containing over 15.7% Ni, represent structure (III) which is characterized by greatly improved creep rupture strength. The higher the nickel content, the higher will be the creep rupture strength. However, if the nickel content exceeds 50%, no further improvement in strength will be obtained, and it will only be adding to the costs.
  • Silicon may be used within the range of 0.01 to 3%. Silicon is added to the molten steel during production for the purpose of deoxidation. Although silicon improves the oxidation resistance of the steel for use at elevated temperatures, greater than 3% will impair weldability and workability, and enhance the formation of a sigma phase.
  • Manganese may be present in amounts of from 0.1 to 10%, also, for the purpose of deoxidation during steel making. Manganese tends to stabilize the austenite and to provent the formation of a sigma phase. If more than 10%, however, is used, oxidation resistance is reduced.
  • Chromium may be present in amounts of from 15 to 35%, also to improve the oxidation resistance of the steel.
  • the chromium content should be at least 15%. However, if greater than 35% is used, such larger amounts can cause difficulties in hot or cold working, and also increase the tendency of sigma phase formation.
  • Co, W, Mo, Nb, Ti, Al and/or N may be further added.
  • Cobalt should be present in amounts of less than 30%. Cobalt will completely dissolve in the matrix of high Cr-high Ni austenite to greatly improve the creep rupture strength. If the level exceeds the cost of the steel will be increased unfavorably.
  • tungsten is used, the quantity present is limited to amounts of below 10%. Tungsten, together with molybdenum, dissolve at the solution heat treatment temperature in the austenite matrix, with a part thereof precipitating in the form of carbides during the slow cooling. The greater amount, however, will remain in solid solution, so that during use, it will precipitate as fine carbide particles within the grains to thereby increase the product strength. However, even if the level is increased beyond 10%, there will be no substantial increased effectiveness, and the hot or cold workability can be impaired.
  • Table 4 compares the structures of steels according to the present invention with certain controls. Those samples were heated at 1,280 C. for 10 minutes after forging, and then slowly cooled to 950 C. for a time ranging from 1.1 second to 1.5 hour.
  • Niobium may be present in amounts of below 5%. It has been a common practice in producing forgings, The addition of niobium is intended to permit the carsuch as producing in forgings of 25 Cr-20Ni type stainbides to precipitate within the grain boundaries during less steel having a carbon level of below 0.1% or in prothe use of steels to thereby improve strength. However, if ducing forgings of Incolloy 800 alloy, or the like, to use the quantity of niobium used is over 5%, the hot workaa solution heat treatment in which the forgings are water bility and weldability will be greatly lmpaired. quenched immediately after the heating at a solution Titanium may be present in amounts of below 5%. Titreatment temperature.
  • Alumlnum may e pr e 1n 3111011018 9 below 5 conventional solution heat treatment
  • the structure (III) Alumlmlm tends to Precipltate 3 dul'lng use at cannot be achieved, even if the carbon level is increased Vated temperatures 1 thereby Increase strength 9 to greater than 1%.
  • the qq of PP 15 cooled by means of helium gas or cool air injection from over the hot werkablhty and weldeblhty W111 be 1,280 (3. down to 950 c.
  • cooling Table 3 describes the structures of steels according to Should occur over a penod of mme than 5 secojlds the present invention, which have been heated to a tom Table 5 shows creep rupture Stmngths at 1,000 for perature of from 1,050 to 1,350" C. for 30 minutes, subsequent to the forging, and then have been slowly cooled to 950 C. for one hour and then water quenched.
  • EXAMPLE 1 shows the results of tests useing steel containing 25% Cr and Ni.
  • the conventional forging material i.e., Sample No. 81
  • Sample No. 80 has an extremely low strength than high carbon casting material, i.e., sample No. 80.
  • Samples Nos. 82 and 84 which have been subjected to the normal TABLE 9 (EXAMPLE 2) Alloy element, percent Type 01 Ni working Heat treatment Creep rupture strength (kg/mm?) C Si Mn 01' 800 0. 900 C. 1,000 C. 1,050 C. Remarks 0.40 1.32 1.06 24. 91 19.92 Casting 6. 3.80 1.90 1.30 Comparative steel.
  • samples Nos. 83 and 85 show extremely high strengths as compared to samples Nos. 81, 82
  • Table 10 shows test results of steels containing 15% Cr and Ni and Table 11 shows such results for steels containing 19% Cr and 41% Ni, respectively.
  • EXAMPLE 2 conventional solution heat treatment, are extremely low Table 9 shows test results using steels containing 25% Cr and 20% Ni. Samples Nos. 92 and 94, which are high carbon steels, have been subjected to conventional solution heat treatment after forging. The conventional low carbon forging steel, sample No. 91, are all lower in strength than the high carbon cast steel of sample No. 90.
  • steel Samples Nos. 1103, 1105, 1203 and 1205 of the present invention afford the same degree of strength as that of the high carbon casting steels of Samples Nos. 1100 and 1200.
  • samples Nos. 93 and 95 present the same degree of strength as that of a high carbon steel No. 90.
  • Samples Nos. 96 and 97 are shown as special EXAMPLE 4 This invention has been essentially described by reference to C-high Cr-high Ni type stainless steel in Examexamples of the present invention.
  • Sample No. 96 was 75 pics 1 to 3.
  • Example 4 illustrates the test results of a W, Mo, Nb, Ti, Al and N, separately.
  • Table 13 shows the test results of the steels containing 27% Cr and 33% Ni, which steels further contain at least two elements of the 27% Cr and 33% Ni, which further contain each of Co,
  • the steels of the present invention exhibit excellent characteristics in the application to forgings, rollings and extrusions. Thesecharacteristics permit the production of tubes having outer diameters of mm. and yet wall thickness of even below 1 mm., which is particularly suited for use as heat exchanger tubes, and they further permit the production of tubes having a length of over 10 m., thus minimizing the number of welding joints which tend to cause trouble during the use of the tubes.
  • the steel of the present invention provides good, sound layers on the inner surface of the tube, thus permitting the use of a tube having a thinner wall thickness with resulting good heat capability, while eliminating the likelihood of rapid carburization of the reducing gas due to imperfections in the tube surfaces.
  • the methods of the present invention permit the production of sheet form steel by ordinary rolling processes.
  • An austenite type heat resistant steel article characterized by high strength properties at elevated temperature consisting essentially of from 0.1 to 1% by weight carbon, from 0.01 to 3% by weight silicon, from 0.01 to 10% by weight manganese, from 13 to 35% by weight chromium, from 15 to 50% by weight nickel, and the balance essentially impurities and iron, wherein a continuous carbide precipitation formed by heat treatment at a temperature of greater than 950 C. is present on the grain boundaries.
  • austenite type heat resistant steel of Claim 1 wherein said steel additionally contains at least one element selected from a group consisting of up to 30% cobalt, up to 10% tungsten, up to 10% molybdenum, up to 5% niobium, up to 5% titanium, up to 5% aluminum and up to 0 .5% nitrogen.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
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US00233255A 1971-03-09 1972-03-09 Austenite type heat-resisting steel having high strength at an elevated temperature and the process for producing same Expired - Lifetime US3826689A (en)

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Cited By (27)

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Publication number Priority date Publication date Assignee Title
US3917493A (en) * 1973-08-13 1975-11-04 Nippon Kokan Kk Austenitic heat resisting steel
DE2606956A1 (de) 1975-12-02 1977-06-16 Pompey Acieries Feuerfeste chrom-nickel-legierung mit hoher oxydations- und karburierungsbestaendigkeit und guter kriechfestigkeit bei sehr hoher temperatur
US4086107A (en) * 1974-05-22 1978-04-25 Nippon Steel Corporation Heat treatment process of high-carbon chromium-nickel heat-resistant stainless steels
US4138279A (en) * 1976-03-01 1979-02-06 Kubota, Ltd. Method of producing stainless steel product
US4221610A (en) * 1978-02-24 1980-09-09 The United States Of America As Represented By The United States Department Of Energy Method for homogenizing alloys susceptible to the formation of carbide stringers and alloys prepared thereby
DE3720055A1 (de) * 1986-07-03 1988-01-07 Haynes Int Inc Korrosionsbestaendiger und verschleissfester stahl
US5064610A (en) * 1989-08-02 1991-11-12 Hitachi Metals, Ltd. Heat resistant steel for use as material of engine valve
EP0467756A1 (fr) * 1990-07-18 1992-01-22 AUBERT & DUVAL Acier austénitique ayant une résistance améliorée à haute température et procédé pour son obtention et la réalisation de pièces mécaniques, en particulier de soupapes
DE3248987C2 (de) * 1981-08-27 1994-06-30 Mitsubishi Materials Corp Verwendung einer Legierung für Führungsschuhe in Warmwalzwerken
EP0837150A1 (en) * 1996-10-21 1998-04-22 Kubota Corporation Heat-resistant alloy steel for hearth metal members of steel material heating furnaces
WO2001086009A1 (fr) * 2000-05-10 2001-11-15 Societe Industrielle De Metallurgie Avancee (S.I.M.A.) Composition d'acier, procede de fabrication et pieces formees dans ces compositions, en particulier soupapes
US6383310B1 (en) * 1999-04-05 2002-05-07 Hitachi Metals, Ltd. Exhaust equipment member, internal combustion engine system using same, and method for producing such exhaust equipment member
US20040031690A1 (en) * 1997-04-17 2004-02-19 Sekisui Chemical Co., Ltd. Conductive particles and method and device for manufacturing the same, anisotropic conductive adhesive and conductive connection structure, and electronic circuit components and method of manufacturing the same
US20040191109A1 (en) * 2003-03-26 2004-09-30 Maziasz Philip J. Wrought stainless steel compositions having engineered microstructures for improved heat resistance
US20060096673A1 (en) * 2002-11-04 2006-05-11 Dominique Flahaut High temperature alloys
US20080008617A1 (en) * 2006-07-07 2008-01-10 Sawford Maria K Wear resistant high temperature alloy
US20080163957A1 (en) * 2007-01-04 2008-07-10 Ut-Battelle, Llc Oxidation resistant high creep strength austentic stainless steel
US20080292489A1 (en) * 2007-01-04 2008-11-27 Ut-Battelle, Llc High Mn Austenitic Stainless Steel
WO2009068722A1 (en) * 2007-11-28 2009-06-04 Metso Lokomo Steels Oy Heat-resistant steel alloy and coiler drum
WO2010043375A1 (de) * 2008-10-13 2010-04-22 Schmidt + Clemens Gmbh + Co. Kg Nickel-chrom-legierung
CN107805764A (zh) * 2016-09-09 2018-03-16 现代自动车株式会社 具有低镍含量的高耐热钢
CN110527913A (zh) * 2019-09-24 2019-12-03 沈阳工业大学 一种新型Fe-Ni-Cr-N合金及制备方法
EP3933064A1 (en) * 2020-07-01 2022-01-05 Garrett Transportation I Inc. Austenitic stainless steel alloys and turbocharger kinematic components formed from stainless steel alloys
US11414734B2 (en) 2018-09-25 2022-08-16 Garrett Transportation I Inc Austenitic stainless steel alloys and turbocharger kinematic components formed from stainless steel alloys
US11479836B2 (en) 2021-01-29 2022-10-25 Ut-Battelle, Llc Low-cost, high-strength, cast creep-resistant alumina-forming alloys for heat-exchangers, supercritical CO2 systems and industrial applications
US11866809B2 (en) 2021-01-29 2024-01-09 Ut-Battelle, Llc Creep and corrosion-resistant cast alumina-forming alloys for high temperature service in industrial and petrochemical applications
US11981875B2 (en) 2018-12-20 2024-05-14 Exxonmobil Chemical Patents Inc. Erosion resistant alloy for thermal cracking reactors

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Cited By (45)

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Publication number Priority date Publication date Assignee Title
US3917493A (en) * 1973-08-13 1975-11-04 Nippon Kokan Kk Austenitic heat resisting steel
US4086107A (en) * 1974-05-22 1978-04-25 Nippon Steel Corporation Heat treatment process of high-carbon chromium-nickel heat-resistant stainless steels
DE2606956A1 (de) 1975-12-02 1977-06-16 Pompey Acieries Feuerfeste chrom-nickel-legierung mit hoher oxydations- und karburierungsbestaendigkeit und guter kriechfestigkeit bei sehr hoher temperatur
US4138279A (en) * 1976-03-01 1979-02-06 Kubota, Ltd. Method of producing stainless steel product
US4221610A (en) * 1978-02-24 1980-09-09 The United States Of America As Represented By The United States Department Of Energy Method for homogenizing alloys susceptible to the formation of carbide stringers and alloys prepared thereby
DE3248987C2 (de) * 1981-08-27 1994-06-30 Mitsubishi Materials Corp Verwendung einer Legierung für Führungsschuhe in Warmwalzwerken
DE3720055A1 (de) * 1986-07-03 1988-01-07 Haynes Int Inc Korrosionsbestaendiger und verschleissfester stahl
US5064610A (en) * 1989-08-02 1991-11-12 Hitachi Metals, Ltd. Heat resistant steel for use as material of engine valve
EP0467756A1 (fr) * 1990-07-18 1992-01-22 AUBERT & DUVAL Acier austénitique ayant une résistance améliorée à haute température et procédé pour son obtention et la réalisation de pièces mécaniques, en particulier de soupapes
FR2664909A1 (fr) * 1990-07-18 1992-01-24 Aubert & Duval Acieries Acier austenitique ayant une resistance amelioree a haute temperature et procede pour son obtention et la realisation de pieces mecaniques, en particulier de soupapes.
AU729085B2 (en) * 1996-10-21 2001-01-25 Kubota Corporation Heat-resistant alloy steel for hearth metal members of steel material furnaces
EP0837150A1 (en) * 1996-10-21 1998-04-22 Kubota Corporation Heat-resistant alloy steel for hearth metal members of steel material heating furnaces
US5882440A (en) * 1996-10-21 1999-03-16 Kubota Corporation Heat-resistant alloy steel for hearth metal members of steel material heating furnaces
US20040031690A1 (en) * 1997-04-17 2004-02-19 Sekisui Chemical Co., Ltd. Conductive particles and method and device for manufacturing the same, anisotropic conductive adhesive and conductive connection structure, and electronic circuit components and method of manufacturing the same
US6383310B1 (en) * 1999-04-05 2002-05-07 Hitachi Metals, Ltd. Exhaust equipment member, internal combustion engine system using same, and method for producing such exhaust equipment member
FR2808807A1 (fr) * 2000-05-10 2001-11-16 Metallurg Avancee Soc Ind De Composition d'acier, procede de fabrication et pieces formees dans ces compositions, en particulier soupapes
US6656418B2 (en) 2000-05-10 2003-12-02 Societe Industrielle De Metallurgie Avancee (S.I.M.A.) Steel composition, method for making same and parts produced from said compositions, particularly valves
WO2001086009A1 (fr) * 2000-05-10 2001-11-15 Societe Industrielle De Metallurgie Avancee (S.I.M.A.) Composition d'acier, procede de fabrication et pieces formees dans ces compositions, en particulier soupapes
US20060096673A1 (en) * 2002-11-04 2006-05-11 Dominique Flahaut High temperature alloys
US20100175508A1 (en) * 2002-11-04 2010-07-15 Dominique Flahaut High temperature alloys
US20040191109A1 (en) * 2003-03-26 2004-09-30 Maziasz Philip J. Wrought stainless steel compositions having engineered microstructures for improved heat resistance
US7258752B2 (en) * 2003-03-26 2007-08-21 Ut-Battelle Llc Wrought stainless steel compositions having engineered microstructures for improved heat resistance
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Publication number Publication date
SU660596A3 (ru) 1979-04-30
NL7203139A (ro) 1972-09-12
GB1381170A (en) 1975-01-22
FR2129518A5 (ro) 1972-10-27
IT975590B (it) 1974-08-10
AT327260B (de) 1976-01-26
DE2211229C3 (de) 1980-01-03
DE2211229A1 (de) 1972-09-21
DE2211229B2 (de) 1979-05-03
CA965994A (en) 1975-04-15
ATA189872A (de) 1975-04-15
BE780455A (fr) 1972-07-03
SE407238B (sv) 1979-03-19
JPS5040099B1 (ro) 1975-12-22

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