EP0387670A1 - Alliage d'acier ferritique - Google Patents

Alliage d'acier ferritique Download PDF

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Publication number
EP0387670A1
EP0387670A1 EP90104300A EP90104300A EP0387670A1 EP 0387670 A1 EP0387670 A1 EP 0387670A1 EP 90104300 A EP90104300 A EP 90104300A EP 90104300 A EP90104300 A EP 90104300A EP 0387670 A1 EP0387670 A1 EP 0387670A1
Authority
EP
European Patent Office
Prior art keywords
alloy
zirconium
titanium
max
contents
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.)
Granted
Application number
EP90104300A
Other languages
German (de)
English (en)
Other versions
EP0387670B1 (fr
Inventor
Ulrich Dr. Heubner
Ulrich Dr. Brill
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.)
Krupp VDM GmbH
Original Assignee
VDM Nickel Technologie AG
Krupp VDM GmbH
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 VDM Nickel Technologie AG, Krupp VDM GmbH filed Critical VDM Nickel Technologie AG
Priority to AT90104300T priority Critical patent/ATE101659T1/de
Publication of EP0387670A1 publication Critical patent/EP0387670A1/fr
Application granted granted Critical
Publication of EP0387670B1 publication Critical patent/EP0387670B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C22C38/24—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
    • 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
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium

Definitions

  • the invention relates to a heat-formable, ferritic steel alloy 20 to 25% chromium 5 to 8% aluminum Max. 0.01% phosphorus Max. 0.01% magnesium Max. 0.5% manganese Max. 0.005% sulfur Rest iron, including inevitable impurities.
  • Alloys of this type are used for the production of electrical heating elements and high-temperature-resistant catalyst supports. They form firmly adhering oxide layers and therefore have very good scaling resistance. Of course, there has been no lack of attempts to further improve the basic composition by adding further elements or by reducing the unavoidable, production-related impurities.
  • GB-A-2 070 642 proposes adding up to 2% yttrium, hafnium, zirconium, cerium or lanthanum and 0.1 to 2% titanium in order to make the casting structure more fine-grained and to improve the hot-formability.
  • the additions of yttrium, hafnium, zirconium and mixed metal (CE + La) should preferably each be up to 1% (claims 7, 8, 10 and 11). The best results are achieved with 0.34% Ti and 0.46% Nb (Example B).
  • the power supply is switched on and off alternately for 2 minutes.
  • the maximum temperature reached is measured optically and kept constant at a constant switching frequency by changing the applied voltage throughout the test period (KE Volk: Nickel and nickel alloys, p. 145, Springer-Verlag, 1970).
  • niobium in ferritic Fe-Cr alloys not only causes a slight increase in embrittlement at 475 ° C (cf. Boron, Calcium, Columbium and Zirconium in Iron and Steel, page 199, John Wiley & Sons, New York, 1966 ), but also worsens the Resistance under cyclically changing oxidation conditions.
  • various niobium oxides Nb, NbO2, Nb2O classroom
  • the high-temperature version of the niobium oxide is not very stable, since its melting point is comparatively low, that is, around 1500 ° C (see P. Kofstad: High Temperature Oxidation of Metals, page 215, John Wiley & Sons, New York, 1966) .
  • the base alloy contains, in addition to 0.002 to 0.06% rare earths and at most 0.04% phosphorus and 0.03% sulfur, zirconium and niobium for stabilizing and improving the fatigue strength.
  • Zr and Nb should then be added up to 1.068 and 1.928% and still up to 0.364 and 1.209% Nb, if carbon and nitrogen should be completely absent (see claim 1).
  • the invention has for its object to further improve the long-known base alloy and to avoid the disadvantages found in the prior art.
  • the grain growth should be significantly restricted and the service life should be significantly improved in the cyclic oxidation test.
  • the alloy with 20 to 25% chromium 5 to 8% aluminum Max. 0.01% phosphorus Max. 0.01% magnesium Max. 0.5% manganese Max.
  • FIG. 1a shows, in a highly simplified manner, a device for checking the service life of a horizontally arranged, helically wound heating conductor (1) which is clamped at the end in a holder (2) and connected to a voltage source (3).
  • the heating conductor consisted of a 50 mm long coil with 12 turns and an inner diameter of 3 mm. The wire diameter was 0.4 mm.
  • the heating conductor was switched on and off in alternation of two minutes, whereby the temperature reached during the heating phase was measured without contact by means of a radiation pyrometer and regulated to a constant value by changing the applied voltage.
  • Fig. 1b shows - also greatly simplified - a device for testing the life of a vertically hanging heating conductor wire (4) of one meter in length, which is clamped at its upper end in a holder (5), loaded with a variable weight (6) and with a voltage source (7) is connected.
  • FIGS. 2 to 5 relate to a comparison alloy (sample 1) and an alloy modified according to the invention (sample 2) of the following composition: Sample 1 Sample 2 Cr 20.10 20.45 Al 4.91 5.05 P 0.009 0.007 Mg ⁇ 0.01 ⁇ 0.01 Mn 0.22 0.15 S 0.003 0.002 Y - 0.04 N 0.010 0.007 C. 0.045 0.037 Ti - 0.07 Zr 0.16 0.06 Fe rest rest rest rest rest rest rest rest rest rest
  • FIG. 2 shows the service life values achieved in a device according to FIG. 1a, expressed by the number of cycles reached until it burns out.
  • the samples were switched on and off for 2 minutes each and the temperature reached during the heating phase was measured without contact and by changing the applied voltage it was ensured that a constant test temperature of 1200 ° C was maintained in each cycle during the entire test period.
  • Sample 1 has endured 5343 cycles, while Sample 2 has only burned out at 6213 cycles. This corresponds to an increase of over 15%.
  • the determined heat resistance values are plotted in FIG. 3 and it can be seen that the alloy modified according to the invention has higher heat resistance values in the entire temperature test range.
  • FIG. 4 shows the number of cycles achieved in a test according to FIG. 1b as a function of the applied voltage.
  • the modified alloy is characterized by a significantly longer service life under all loads. With a tension of 2 N / mm2 the service life is 6 times, with 3 N / mm2 almost 5 times and with 4 N / mm2 still 3.5 times longer.
  • the ductility of a material after long-term use at high temperatures is also an important design feature.
  • the decrease in ductility in ferritic Fe-Cr-Al alloys is due to the strong grain growth at high temperatures.
  • 5a shows the grain size values for sample 1 after 6.5 days of aging at 950 to 1050 ° C. in ⁇ m (upper curve).
  • the grain size values for the modified alloy are given after an aging period of 13 days at 950, 1050 and 1150 ° C (lower curve). It is readily apparent that the modified alloy is significantly more fine-grained than the comparative alloy even when the aging time is twice as long.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Resistance Heating (AREA)
  • Catalysts (AREA)
  • Heat Treatment Of Steel (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Laminated Bodies (AREA)
  • Soft Magnetic Materials (AREA)
EP90104300A 1989-03-16 1990-03-07 Alliage d'acier ferritique Expired - Lifetime EP0387670B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90104300T ATE101659T1 (de) 1989-03-16 1990-03-07 Ferritische stahllegierung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3908526 1989-03-16
DE3908526A DE3908526A1 (de) 1989-03-16 1989-03-16 Ferritische stahllegierung

Publications (2)

Publication Number Publication Date
EP0387670A1 true EP0387670A1 (fr) 1990-09-19
EP0387670B1 EP0387670B1 (fr) 1994-02-16

Family

ID=6376432

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90104300A Expired - Lifetime EP0387670B1 (fr) 1989-03-16 1990-03-07 Alliage d'acier ferritique

Country Status (13)

Country Link
EP (1) EP0387670B1 (fr)
JP (1) JPH03166341A (fr)
KR (1) KR960011803B1 (fr)
AT (1) ATE101659T1 (fr)
AU (1) AU621998B2 (fr)
BR (1) BR9001241A (fr)
CA (1) CA2012065A1 (fr)
DD (1) DD298950A5 (fr)
DE (2) DE3908526A1 (fr)
ES (1) ES2051399T3 (fr)
IE (1) IE63312B1 (fr)
MX (1) MX173057B (fr)
ZA (1) ZA901809B (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0573343A1 (fr) * 1992-06-01 1993-12-08 Sumitomo Chemical Company, Limited Tôles et feuilles en acier ferritique inoxydable et procédé pour leur fabrication
GB2285058A (en) * 1993-12-24 1995-06-28 Ceramaspeed Ltd Alloy for radiant electric heater
EP0646657A4 (fr) * 1993-03-19 1995-07-05 Nippon Yakin Kogyo Co Ltd Acier ferritique inoxydable presentant une excellente resistance a l'oxydation.
EP0735153A1 (fr) * 1995-03-29 1996-10-02 USINOR SACILOR Société Anonyme Acier inoxydable ferritique, utilisable notamment pour des supports de catalyseurs
DE19642497C1 (de) * 1996-10-15 1997-07-24 Krupp Vdm Gmbh Verfahren zur Herstellung einer Eisen-Chrom-Aluminium-Folie und ihre Verwendung
DE19743720C1 (de) * 1997-10-02 1998-12-24 Krupp Vdm Gmbh Verfahren zur Herstellung einer oxidationsbeständigen Metallfolie und deren Verwendung
WO2000008223A1 (fr) * 1998-07-31 2000-02-17 Krupp Vdm Gmbh Feuille metallique resistant a l'oxydation
WO2001000896A1 (fr) * 1999-06-24 2001-01-04 Krupp Vdm Gmbh Alliage fe-cr-al
DE10002933C1 (de) * 2000-01-25 2001-07-05 Krupp Vdm Gmbh Verfahren zur Herstellung einer formstabilen Eisen-Chrom-Aluminium-Folie sowie Verwendung derselben
DE10310865B3 (de) * 2003-03-11 2004-05-27 Thyssenkrupp Vdm Gmbh Eisen-Chrom-Aluminium-Legierung
WO2006083161A1 (fr) * 2004-11-23 2006-08-10 Ferro Techniek Holding B.V. Composition d'email, ensemble et utilisation de celle-ci sur une surface de substrat
US8580190B2 (en) 2008-04-10 2013-11-12 Outokumpu Vdm Gmbh Durable iron-chromium-aluminum alloy showing minor changes in heat resistance

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007005154B4 (de) 2007-01-29 2009-04-09 Thyssenkrupp Vdm Gmbh Verwendung einer Eisen-Chrom-Aluminium-Legierung mit hoher Lebensdauer und geringen Änderungen im Warmwiderstand
CN104233083A (zh) * 2014-08-26 2014-12-24 盐城市鑫洋电热材料有限公司 一种析出强化电热合金及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2191790A (en) * 1938-05-07 1940-02-27 Electro Metallurg Co Steels and electrical resistance elements
DE2031495A1 (de) * 1969-06-25 1971-01-07 To> o Kog\o Co , Ltd , Hiroshima, Tokyo Shibaura Electric Co . Ltd . Kawa saki, (Japan) Verfahren zur Herstellung korrosions bestandiger Gegenstande aus Metall
GB2070642A (en) * 1980-02-28 1981-09-09 Firth Brown Ltd Ferritic iron-aluminium- chromium alloys
EP0035369A1 (fr) * 1980-02-28 1981-09-09 Sheffield Forgemasters Limited Alliages ferritiques de fer-aluminium-chrome
GB2160892A (en) * 1984-06-08 1986-01-02 Osaka Prefecture Fe-Cr-A l type implant alloy for medical treatment
EP0290719A1 (fr) * 1987-02-27 1988-11-17 Thyssen Edelstahlwerke AG Demi-produit en acier ferritique et ses utilisations

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2191790A (en) * 1938-05-07 1940-02-27 Electro Metallurg Co Steels and electrical resistance elements
DE2031495A1 (de) * 1969-06-25 1971-01-07 To> o Kog\o Co , Ltd , Hiroshima, Tokyo Shibaura Electric Co . Ltd . Kawa saki, (Japan) Verfahren zur Herstellung korrosions bestandiger Gegenstande aus Metall
GB2070642A (en) * 1980-02-28 1981-09-09 Firth Brown Ltd Ferritic iron-aluminium- chromium alloys
EP0035369A1 (fr) * 1980-02-28 1981-09-09 Sheffield Forgemasters Limited Alliages ferritiques de fer-aluminium-chrome
GB2160892A (en) * 1984-06-08 1986-01-02 Osaka Prefecture Fe-Cr-A l type implant alloy for medical treatment
EP0290719A1 (fr) * 1987-02-27 1988-11-17 Thyssen Edelstahlwerke AG Demi-produit en acier ferritique et ses utilisations

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DRAHT, Band 36, Nr. 11, November 1985, Seiten 536-540, Bamberg, DE; A. GIEREK et al.: "Der Yttiumeinfluss auf die Hitzebeständigkeit und die Dauerhaftigkeit von Widerstands-Heizdrähten aus Fe-Cr-Al-Stählen" *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5340415A (en) * 1992-06-01 1994-08-23 Sumitomo Metal Industries, Ltd. Ferritic stainless steel plates and foils and method for their production
EP0573343A1 (fr) * 1992-06-01 1993-12-08 Sumitomo Chemical Company, Limited Tôles et feuilles en acier ferritique inoxydable et procédé pour leur fabrication
EP0646657A4 (fr) * 1993-03-19 1995-07-05 Nippon Yakin Kogyo Co Ltd Acier ferritique inoxydable presentant une excellente resistance a l'oxydation.
US5480608A (en) * 1993-03-19 1996-01-02 Nippon Yakin Kogyo Co., Ltd. Ferritic stainless steel having an excellent oxidation resistance
GB2285058A (en) * 1993-12-24 1995-06-28 Ceramaspeed Ltd Alloy for radiant electric heater
GB2285058B (en) * 1993-12-24 1997-01-08 Ceramaspeed Ltd Radiant Electric Heater
US5866065A (en) * 1995-03-29 1999-02-02 Usinor Sacilor Ferritic stainless steel of use in particular for catalyst supports
EP0735153A1 (fr) * 1995-03-29 1996-10-02 USINOR SACILOR Société Anonyme Acier inoxydable ferritique, utilisable notamment pour des supports de catalyseurs
FR2732360A1 (fr) * 1995-03-29 1996-10-04 Ugine Savoie Sa Acier inoxydable ferritique utilisable, notamment pour des supports de catalyseurs
DE19642497C1 (de) * 1996-10-15 1997-07-24 Krupp Vdm Gmbh Verfahren zur Herstellung einer Eisen-Chrom-Aluminium-Folie und ihre Verwendung
DE19743720C1 (de) * 1997-10-02 1998-12-24 Krupp Vdm Gmbh Verfahren zur Herstellung einer oxidationsbeständigen Metallfolie und deren Verwendung
WO2000008223A1 (fr) * 1998-07-31 2000-02-17 Krupp Vdm Gmbh Feuille metallique resistant a l'oxydation
WO2001000896A1 (fr) * 1999-06-24 2001-01-04 Krupp Vdm Gmbh Alliage fe-cr-al
DE10002933C1 (de) * 2000-01-25 2001-07-05 Krupp Vdm Gmbh Verfahren zur Herstellung einer formstabilen Eisen-Chrom-Aluminium-Folie sowie Verwendung derselben
DE10310865B3 (de) * 2003-03-11 2004-05-27 Thyssenkrupp Vdm Gmbh Eisen-Chrom-Aluminium-Legierung
WO2006083161A1 (fr) * 2004-11-23 2006-08-10 Ferro Techniek Holding B.V. Composition d'email, ensemble et utilisation de celle-ci sur une surface de substrat
US8580190B2 (en) 2008-04-10 2013-11-12 Outokumpu Vdm Gmbh Durable iron-chromium-aluminum alloy showing minor changes in heat resistance

Also Published As

Publication number Publication date
MX173057B (es) 1994-01-31
KR960011803B1 (ko) 1996-08-30
ATE101659T1 (de) 1994-03-15
DE59004570D1 (de) 1994-03-24
AU5133390A (en) 1990-09-27
KR900014614A (ko) 1990-10-24
ES2051399T3 (es) 1994-06-16
IE63312B1 (en) 1995-04-05
DE3908526A1 (de) 1990-09-20
EP0387670B1 (fr) 1994-02-16
AU621998B2 (en) 1992-03-26
ZA901809B (en) 1991-04-24
DD298950A5 (de) 1992-03-19
JPH0581657B2 (fr) 1993-11-15
BR9001241A (pt) 1991-03-26
IE900819L (en) 1990-09-16
CA2012065A1 (fr) 1990-09-16
JPH03166341A (ja) 1991-07-18

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