EP0688882A1 - Aluminium plattiertes rostfreies stahlblech mit hervorragender hochtemperaturoxidationsbeständigkeit - Google Patents

Aluminium plattiertes rostfreies stahlblech mit hervorragender hochtemperaturoxidationsbeständigkeit Download PDF

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Publication number
EP0688882A1
EP0688882A1 EP95903983A EP95903983A EP0688882A1 EP 0688882 A1 EP0688882 A1 EP 0688882A1 EP 95903983 A EP95903983 A EP 95903983A EP 95903983 A EP95903983 A EP 95903983A EP 0688882 A1 EP0688882 A1 EP 0688882A1
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EP
European Patent Office
Prior art keywords
stainless steel
aluminum
steel sheet
oxidation resistance
temperature oxidation
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
EP95903983A
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English (en)
French (fr)
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EP0688882A4 (de
Inventor
Atsushi Ando
Toshiharu Kitsutaka
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 Nisshin Co Ltd
Original Assignee
Nisshin Steel Co 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 Nisshin Steel Co Ltd filed Critical Nisshin Steel Co Ltd
Publication of EP0688882A1 publication Critical patent/EP0688882A1/de
Publication of EP0688882A4 publication Critical patent/EP0688882A4/de
Ceased legal-status Critical Current

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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
    • 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
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium

Definitions

  • the present invention relates to an Al-coated stainless steel sheet that has very good high-temperature oxidation resistance.
  • Al-coated stainless steel formed by coating stainless steel with aluminum or an aluminum-based alloy, exhibits good resistance to heat and corrosion, and therefore is used extensively in applications in which resistance to heat and/or corrosion is required.
  • Typical heat-resistance applications include combustion equipment, heating equipment, and automotive exhaust system tubing and exhaust cleaning devices (catalytic support).
  • JP-A-61-281861 discloses adding Al to the base steel of the foil
  • JP-A-62-11547 discloses the addition of Al and Ti
  • JP-A-HEI-5-140766 discloses the addition of rare earth metals and/or Y
  • JP-A-HEI-1-159384 discloses the addition of Al and rare earth metals and/or Y.
  • JP-A-HEI-5-112859 it was shown that the corrosion-resistance of automotive exhaust system mufflers of Al-coated stainless steel in an exhaust gas condensation (condensate) environment could be improved by adding an appropriate amount of Mo to the base ferritic stainless steel sheet material.
  • abnormal oxidization refers to local peeling and splitting of a heat-resistant, protective layer of Al or Cr oxides or the like formed on an Al-coated stainless steel sheet surface, leading to the rapid advance of oxidation, the abnormal spread of ferric oxides and the sudden loss of heat resistance.
  • the object of the present invention is therefore to provide Al-coated stainless steel sheet having better high-temperature oxidation resistance that does not exhibit abnormal oxidation in a high-temperature oxidising atmosphere that is more severe than that which can be withstood by conventional heat-resistant Al-coated stainless steel sheet.
  • an Al-coated stainless steel sheet having good high-temperature oxidation resistance formed by coating a ferritic stainless steel sheet with aluminum or aluminum-based alloy, said steel comprising, by weight: up to 0.05% C, up to 1.0% Si, up to 1.0% Mn, from 10.0% to 30.0% Cr, up to 0.05% N, from 0.1% to 4.0% Mo, a total of from 0.01% to 0.2% of one or more elements selected from a group comprised of rare earth metals and Y, a total of (%C + %N) x 4.0% to 0.8% of one or more elements selected from a group comprised of Ti, Nb, V, and Zr, and optionally containing up to 6.0% Al, the balance being iron and unavoidable impurities.
  • Figure 1 is a graph illustrating the relationship between Mo content and time taken for abnormal oxidation to arise in Al-coated stainless steel in a first example of the invention.
  • the Al-coated stainless steel sheet according to the present invention exhibits high-temperature oxidation resistance at higher temperatures than those achievable with conventional heat-resistant Al-coated stainless steel sheet. Moreover, as shown hereinbelow in the examples, even Al-coated stainless steel sheet that is very thin, such as for example stainless steel foil only 50 ⁇ m thick, does not exhibit abnormal oxidation even after being left for an extended period of time in an oxidising atmosphere at a temperature of from 1150°C to 1250°C. Such properties cannot be obtained with Al-coated stainless steel sheets of the prior art.
  • the excellent high-temperature oxidation resistance of the Al-coated stainless steel sheet of this invention results from using ferritic stainless steel sheet having the above composition as the base steel sheet.
  • ferritic stainless steel sheet having the above composition as the base steel sheet.
  • including appropriate amounts of rare earth metals or Y, or both, and Mo is useful for imparting high-temperature oxidation resistance.
  • Mo improves the high-temperature strength of ferritic stainless steel and is also effective for improving the corrosion resistance of ferritic stainless steel.
  • the Mo in the steel does not form surface oxides that are stable at high temperatures.
  • Mo has been considered an element that does not contribute to improving high-temperature oxidation resistance, but has been considered an element that actually degrades the high-temperature oxidation resistance of the steel.
  • a suitable amount of Mo in the steel functions to promote the formation of a dense aluminum oxide layer that has good adhesion to the base steel, markedly suppress the decrease of Al in the steel and promote the formation of a chromium oxide film when the Al in the steel has decreased, and that, taken together, the overall effect is to contribute to markedly raise the high-temperature oxidation resistance of the Al-coated stainless steel sheet concerned.
  • Aluminum based alloy refers to the aluminum based alloy coating that is commonly applied to ferritic stainless steel, and more specifically, to aluminum based alloy coating in which the aluminum contains up to 11% by weight silicon. In some cases, the aluminum may contain Mn, Mg, Cr or the like as alloying elements. As used herein, Al-coated is a general term encompassing aluminum coating and aluminum based alloy coating.
  • a low C content in the base steel sheet is preferable. Carbon in the steel has the effect of obstructing the diffusion of aluminum from the aluminum coating into the base steel, when the Al-coated stainless steel sheet is heated. Thus, a base steel C content of up to 0.05% by weight, and preferably up to 0.03%, is specified. However, since the amount of solid solution C having the above effect is decreased by the addition of elements such as Ti, Nb, V, and Zr that form compounds with C and N in the steel, no upper limit is specified for the C content.
  • Si hardens the steel and reduces the toughness, so a Si content not exceeding 1.0% by weight is preferable.
  • Cr is a basic component for obtaining Al-coated steel sheet that has high-temperature oxidation resistance, for which at least 10% Cr is required.
  • a Cr content that exceeds 30% does not result in any marked improvement in the effect, and too much Cr can degrade the workability. Therefore, a base steel Cr content of from 10% to 30% by weight is specified.
  • N combines with Al diffused into the base steel from the aluminum coating layer to form AlN, which hinders the diffusion of Al.
  • a low N content is therefore preferable, and so a N content of up to 0.05% by weight is specified.
  • the amount of solid solution N having the above effect is decreased by the addition of elements such as Ti, in such cases no upper limit is specified for the N content.
  • Mo plays a very important role in increasing the high-temperature oxidation resistance of Al-coated stainless steel sheet. As described in the following examples, this effect is manifested when the Mo content is at least 0.1%. However, an amount of Mo that exceeds 4% degrades the toughness of stainless steel and makes it more difficult to produce.
  • the Mo content in the base stainless steel is therefore set at from 0.1% to 4.0% by weight, and more preferably at from 0.5% to 4.0% by weight.
  • Rare earth metals and Y have the effect of improving the adhesion of the aluminum oxide film formed on the surface of Al-coated steel sheet. This effect is manifested when a total of at least 0.01% by weight of one or more elements selected from the rare earth metals and Y is added. However, a total added amount that exceeds 0.2% gives rise to the precipitation of inclusions in the base steel, degrading the high-temperature oxidation resistance. Therefore, the total content of one or more elements selected from a group comprised of rare earth metals and Y has been set at from 0.01 to 0.2 wt%.
  • Ti, Nb, V, and Zr each form compounds with C and N in the steel, thereby fixing the carbon and nitrogen.
  • the aluminum in the aluminum coating forms the principal source of the aluminum for the aluminum oxide film.
  • the amount of aluminum normally used as a deoxidizing agent during the steelmaking process is sufficient.
  • Adding aluminum to the base stainless steel can further enhance the high-temperature oxidation resistance.
  • an Al content that exceeds 6% can degrade the toughness of the slab and hot-rolled strip, making it difficult to produce the steel.
  • the base stainless steel can be given up to 6.0 wt% Al.
  • the Al-coated stainless steel sheet according to this invention comprises aluminum coated or aluminum alloy coated ferritic stainless steel sheet having the above components and composition. Compared to conventional Al-coated stainless steel sheet material, the Al-coated stainless steel sheet of this invention can withstand severer high-temperature oxidation conditions without exhibiting abnormal oxidation. Any method can be used to effect the aluminum or aluminum alloy coating that ensures good adhesion with the base stainless steel. Evaporation and electroplating are examples of suitable coating methods. In some cases, cladding or spraying may be used.
  • Stainless steel foils 50 ⁇ m thick having the compositions shown in Table 1 were prepared. Both sides of the foils were then given a 3- ⁇ m-thick coating of aluminum by evaporation, the foils were subjected to oxidation tests by being maintained at 1150° C under atmospheric conditions, and the effect of Mo content on the abnormal oxidation onset time was investigated. Table 1 also lists the results. The abnormal oxidation onset time is shown as total heating time, from when a test specimen is removed from the furnace and the surface visually inspected to the point at which brown, ridged oxides are observed in addition to the normal thin, protective, uniform oxide layer.
  • Figure 1 is a graph of the relationship between abnormal oxidation onset time and steel Mo content.
  • Table 1 and Figure 1 reveal that the abnormal oxidation onset time gets longer as the Mo content is increased, and that this effect starts to occur when the Mo content is in the order of 0.1%. This is considered to be caused by the added Mo suppressing the growth of the aluminum oxide film.
  • the marked improvement in oxidation resistance at such a high temperature shows that the aluminum diffused in the steel foil does not become exhausted for an extended period of time. Expressed another way, it can be considered that the growth of the aluminum oxide film is effectively suppressed owing to the existence of Mo. Whatever the reason, in the case of the steel of the comparative specimen (No.
  • 0.3-mm-thick stainless steel sheet having the composition shown in Table 2 was given an approximately 150 g/m2 coating of Al - 9.5% Si alloy by the aluminum hot dip method, and then rolled to form Al-coated stainless steel foil 50 ⁇ m thick. As in Example 1, the foils were then subjected to oxidation tests by being maintained at 1150°C under atmospheric conditions. Table 1 also lists the time it took for each of the tested Al-coated stainless steel foils to exhibit abnormal oxidation.
  • Table 2 shows that in each of the inventive specimens (Nos. 6 to 12) in which the amount of each component in the base steel is within the range according to this invention, abnormal oxidation onset time is over 500 hours, indicating a marked improvement in the high-temperature oxidation resistance.
  • comparative specimen No. 13 in which the Cr content is less than 10 wt%
  • comparative specimen No. 14 in which the total content of rare earth metals and Y is less than 0.01 wt%
  • comparative specimen No. 15 in which the C content and N content are each over 0.05 wt%
  • the abnormal oxidation onset time is a short 400 hours or less.
  • Table 3 shows that each of the Al-coated steel foils according to the invention exhibited an abnormal oxidation onset time of over 1000 hours, indicating a marked improvement in the high-temperature oxidation resistance of the material.
  • the abnormal oxidation onset time in the case of steel foil that had not been Al-coated was a relatively short 400 hours or less.
  • Ferritic stainless steel sheets No. 5 and No. 1 (each 0.25 mm thick) listed in Table 1 were given a 200 g/m2 coating of Al - 9% Si alloy by the aluminum hot dip method, and then rolled to form Al-coated stainless steel foil 50 ⁇ m thick. The foils were then subjected to the same oxidation tests as Example 1 at a temperature of from 1150°C to 1250°C and the abnormal oxidation onset times investigated. The results are listed in Table 4.
  • the base steels Nos. 5 and 1 of the Al-coated stainless steel foils have the same composition contents, except for Mo, which is contained in steel No. 5 but not in steel No. 1.
  • Table 4 at each temperature the Mo-containing steel No. 5 exhibits a far longer abnormal oxidation onset time than steel No. 1 which does not contain Mo.
  • At 1250° C steel No. 5 exhibited an abnormal oxidation onset time of 350 hours, providing a high-temperature oxidation resistance not attainable with the conventional steel material.
  • Al-coated stainless steel sheet that can withstand use under high-temperature conditions that are beyond the ability of conventional Al-coated stainless steel sheet to withstand.
  • the present invention can expand the range of application of such steel materials to turbine peripheral materials, boiler materials, catalytic metal support materials used in exhaust gas cleaning devices for high-temperature engines, and other such fields.

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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 Sheet Steel (AREA)
  • Catalysts (AREA)
EP95903983A 1993-12-28 1994-12-27 Aluminium plattiertes rostfreies stahlblech mit hervorragender hochtemperaturoxidationsbeständigkeit Ceased EP0688882A4 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP34903193 1993-12-28
JP349031/93 1993-12-28
PCT/JP1994/002245 WO1995018241A1 (fr) 1993-12-28 1994-12-27 Tole d'acier inoxydable plaquee d'aluminium presentant une excellente resistance a l'oxydation a haute temperature

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EP0688882A1 true EP0688882A1 (de) 1995-12-27
EP0688882A4 EP0688882A4 (de) 1996-03-27

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EP95903983A Ceased EP0688882A4 (de) 1993-12-28 1994-12-27 Aluminium plattiertes rostfreies stahlblech mit hervorragender hochtemperaturoxidationsbeständigkeit

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EP (1) EP0688882A4 (de)
WO (1) WO1995018241A1 (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000008223A1 (de) * 1998-07-31 2000-02-17 Krupp Vdm Gmbh Oxidationsbeständige metallfolie
FR2807069A1 (fr) * 2000-03-29 2001-10-05 Usinor Tole en acier inoxydable ferritique revetue utilisable dans le domaine de l'echappement d'un moteur de vehicule automobile
WO2005024093A1 (en) * 2003-09-05 2005-03-17 Sandvik Intellectual Property Ab A stainless steel strip coated with aluminium
WO2005080622A1 (en) * 2004-02-23 2005-09-01 Sandvik Intellectual Property Ab Cr-al-steel for high-temperature applications
WO2009045136A1 (en) * 2007-10-05 2009-04-09 Sandvik Intellectual Property Ab The use and method of producing a dispersion strengthened steel as material in a roller for a roller hearth furnace
US20220056547A1 (en) * 2018-09-13 2022-02-24 Jfe Steel Corporation Ferritic stainless steel sheet and method of producing same, and al or al alloy coated stainless steel sheet
US12116672B2 (en) 2019-06-19 2024-10-15 Jfe Steel Corporation Al or Al alloy-coated stainless steel sheet and method of manufacturing ferritic stainless steel sheet

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU515825A1 (ru) * 1974-05-13 1976-05-30 Предприятие П/Я В-2120 Ферритна сталь
EP0435003A1 (de) * 1989-11-29 1991-07-03 Nippon Steel Corporation Rostfreier Stahl mit ausgezeichneter Korrosionsbeständigkeit zur Verwendung in Auspuffsystemen von Motoren
EP0516267A1 (de) * 1991-05-29 1992-12-02 Nisshin Steel Co., Ltd. Ferritischer, rostfreier Stahl mit hohem Aluminiumgehalt
EP0573343A1 (de) * 1992-06-01 1993-12-08 Sumitomo Chemical Company, Limited Feinbleche und Folie aus ferritisches rostfreies Stahl und Verfahren zu ihrer Herstellung

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02179853A (ja) * 1988-12-29 1990-07-12 Kawasaki Steel Corp 電気メッキ用フェライト系ステンレス鋼
JPH0621323B2 (ja) * 1989-03-06 1994-03-23 住友金属工業株式会社 耐食、耐酸化性に優れた高強度高クロム鋼
JPH04362127A (ja) * 1991-06-10 1992-12-15 Nisshin Steel Co Ltd 高Ａｌ含有フェライト系ステンレス鋼帯の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU515825A1 (ru) * 1974-05-13 1976-05-30 Предприятие П/Я В-2120 Ферритна сталь
EP0435003A1 (de) * 1989-11-29 1991-07-03 Nippon Steel Corporation Rostfreier Stahl mit ausgezeichneter Korrosionsbeständigkeit zur Verwendung in Auspuffsystemen von Motoren
EP0516267A1 (de) * 1991-05-29 1992-12-02 Nisshin Steel Co., Ltd. Ferritischer, rostfreier Stahl mit hohem Aluminiumgehalt
EP0573343A1 (de) * 1992-06-01 1993-12-08 Sumitomo Chemical Company, Limited Feinbleche und Folie aus ferritisches rostfreies Stahl und Verfahren zu ihrer Herstellung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9518241A1 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000008223A1 (de) * 1998-07-31 2000-02-17 Krupp Vdm Gmbh Oxidationsbeständige metallfolie
FR2807069A1 (fr) * 2000-03-29 2001-10-05 Usinor Tole en acier inoxydable ferritique revetue utilisable dans le domaine de l'echappement d'un moteur de vehicule automobile
US6582835B2 (en) 2000-03-29 2003-06-24 Usinor Coated ferrite stainless steel sheet usable in the automobile exhaust sector
WO2005024093A1 (en) * 2003-09-05 2005-03-17 Sandvik Intellectual Property Ab A stainless steel strip coated with aluminium
WO2005080622A1 (en) * 2004-02-23 2005-09-01 Sandvik Intellectual Property Ab Cr-al-steel for high-temperature applications
WO2009045136A1 (en) * 2007-10-05 2009-04-09 Sandvik Intellectual Property Ab The use and method of producing a dispersion strengthened steel as material in a roller for a roller hearth furnace
US8597438B2 (en) 2007-10-05 2013-12-03 Sandvik Intellectual Property Ab Use and method of producing a dispersion strengthened steel as material in a roller for a roller hearth furnace
US20220056547A1 (en) * 2018-09-13 2022-02-24 Jfe Steel Corporation Ferritic stainless steel sheet and method of producing same, and al or al alloy coated stainless steel sheet
US12116672B2 (en) 2019-06-19 2024-10-15 Jfe Steel Corporation Al or Al alloy-coated stainless steel sheet and method of manufacturing ferritic stainless steel sheet

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EP0688882A4 (de) 1996-03-27
WO1995018241A1 (fr) 1995-07-06

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