EP0609682A1 - Alliage résistant à l'oxydation et à la corrosion, à base l'aluminiure de fer dopé et application de cet alliage - Google Patents

Alliage résistant à l'oxydation et à la corrosion, à base l'aluminiure de fer dopé et application de cet alliage Download PDF

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Publication number
EP0609682A1
EP0609682A1 EP94100485A EP94100485A EP0609682A1 EP 0609682 A1 EP0609682 A1 EP 0609682A1 EP 94100485 A EP94100485 A EP 94100485A EP 94100485 A EP94100485 A EP 94100485A EP 0609682 A1 EP0609682 A1 EP 0609682A1
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EP
European Patent Office
Prior art keywords
alloy
oxidation
corrosion
boron
iron
Prior art date
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Application number
EP94100485A
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German (de)
English (en)
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EP0609682B1 (fr
Inventor
Mohamed Y. Dr. Nazmy
Corrado Noseda
Markus Staubli
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.)
ABB Schweiz AG
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ABB Management AG
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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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium

Definitions

  • Oxidation- and corrosion-resistant alloys based on doped iron aluminide Fe3Al can be used in parts of thermal machines that are subjected to high thermal loads and are subject to oxidizing and / or corrosive effects. There, they are expected to increasingly replace oxide dispersion-hardened steels and nickel-based superalloys.
  • the invention is based on an oxidation and corrosion-resistant alloy according to the introductory part of claim 1.
  • an alloy known for example from US Pat. No. 5,158,744 A, contains as components 24 to 28 at% aluminum, 0.1 to 2 at% niobium, 0 , 1 to 10 at% chromium, 0.1 to 1 at% boron, 0.1 to 2 at% silicon and the balance iron.
  • the known alloy is characterized in the temperature range between 300 and 700 ° C by a high resistance to oxidation and corrosion as well as sufficient heat resistance. At room temperature, this alloy also has sufficient ductility for many applications.
  • the invention is based on the object of developing an alloy based on doped iron aluminide which is distinguished by a high resistance to oxidation and corrosion, even at temperatures above 700 ° C.
  • the object of the invention is also a suitable application of this alloy.
  • the alloy according to the invention is characterized by an oxidation and corrosion resistance which generally far exceeds that of prior art alloys.
  • the alloy according to the invention can be produced very inexpensively by casting or by casting and rolling.
  • Another advantage of the alloy according to the invention is that its components exclusively contain metals, which are comparatively inexpensive and are available regardless of strategic-political influence.
  • the alloy according to the invention also has a comparatively low density of only 6.5 g / cm 3 for certain applications in thermal turbomachines with sufficient strength and ductility.
  • Alloys I, II, III and IV shown in the figure have the following compositions: Alloy I (alloy according to a preferred embodiment of the invention): component % By weight At% aluminum 16.38 28 niobium 2.01 1 chrome 5.64 5 Silicon 0.61 1 boron 0.74 3.15 titanium 1.38 1.33 iron rest rest Alloy II (under the trademark "Incoloy” and the designation MA 956 commercially available, oxidation and corrosion-resistant alloy with good properties at high temperatures): 20% chromium, 4.5% aluminum, 0.5% titanium, 0.5% yttrium oxide Y2O3, the rest iron Alloy III (prior art alloy according to US 5,158,744 A): component % By weight At% aluminum 15.92 28 niobium 1.96 1 chrome 5.48 5 Silicon 0.56 1 boron 0.11 0.5 iron rest rest Alloy IV (under the trademark "Hastelloy” and the designation X commercially available, oxidation and corrosion-resistant alloy with good properties at high temperatures): 22% chrom
  • the individual elements with a degree of purity of more than 99% served as starting materials.
  • the melt was poured into a cast body of approximately 60 mm in diameter and approximately 80 mm in height.
  • the cast body was melted again under vacuum and also under vacuum in the form of round bars with a diameter of approx. 12 mm and a length of approx. 150 mm or in the form of carrots with a minimum diameter of approx. 12 mm and a maximum diameter of approx. 30 mm and a length of approx. 120 mm. From this and from alloys II and IV, test specimens for tensile tests and platelets with a surface area of a few cm2 and a thickness of approximately 1-2 mm were produced.
  • alloys II and IV had better tensile strength, elongation and elongation at break properties than alloy I. However, this had a greater elongation at break than the two alloys II and IV above the aforementioned temperature range.
  • the platelets of alloys I, II, III and IV produced from the castings were heated to 1200 ° C. in air.
  • the mass loss or mass increase caused by oxidation and / or corrosion of each of the platelets was determined thermogravimetrically after certain time steps, in particular after approximately 15, 30, 108, 130, 145 and 500 h .
  • the oxidation and corrosion behavior of the alloys I to IV simulated by the quotient ⁇ W / A0 is shown as a function of the time t [h] at an ambient temperature of 1200 ° C. From this it can be seen that at 1200 ° C the alloy IV is strongly oxidized and / or corroded after only a few hours. After 500 h, the alloy III is already twice as strongly oxidized and / or corroded as the alloy I designed according to the invention, whereas the comparatively expensive alloy II, which is difficult to process because of its non-castability, has an oxidation and / or corrosion resistance comparable to that of the alloy I. 1200 ° C.
  • a corresponding oxidation and corrosion resistance can also be found in an alloy designed according to the invention, which has the same constituents as alloy I, but additionally contains 300 ppm carbon and 100 ppm zirconium. This alloy is also characterized by slightly increased strength and improved weldability.
  • the alloy according to the invention has good oxidation and corrosion resistance when the aluminum content is at least 24 and at most 28 at%. If the aluminum content drops below 24 at%, the oxidation and corrosion resistance of the alloy according to the invention deteriorates. If the aluminum content is greater than 28 at%, the alloy becomes increasingly brittle.
  • Alloying 0.1 to 2 at% of niobium increases the hardness and strength of the alloy according to the invention.
  • the elasticity (elongation at break) passes through a maximum when 1 at% niobium is added.
  • tungsten and / or tantalum can also be added in a proportion of 0.1 to 2 at%.
  • a proportion of 0.1 to 2 at% silicon improves the castability of the alloy according to the invention and has a favorable effect on its resistance to oxidation and corrosion. Silicon also increases hardness.
  • the oxidation and corrosion resistance of the alloy according to the invention is considerably improved. This is primarily due to the fact that finely divided titanium diboride TiB2 then forms in the alloy.
  • a protective layer predominantly containing aluminum oxides forms on the surface of the alloy according to the invention.
  • the titanium diboride phase contributes to a substantial stabilization of this protective layer by the titanium diboride phase engaging in the protective layer, for example in the form of acicular crystallites from the alloy, and thereby causing the protective layer to adhere particularly well to the underlying alloy.
  • the proportion of boron should not be more than 5 at% and that of titanium should not be more than 2 at%, since otherwise too much titanium diboride will form and the alloy will become brittle. If the boron content is less than 0.1 at% and that of titanium is less than 0.01 at%, the resistance to oxidation and corrosion deteriorates the alloy according to the invention quite considerably. A boron content of more than 1 at%, but not more than 5 at%, has proven very successful.
  • alloy according to the invention with the following alloy components: aluminum 26 to 28 at% niobium 0.5 to 1.5 at% chrome 3 to 7 at% Silicon 0.5 to 1.5 at% boron 2 to 4 at% titanium 0.5 to 1.5 at% Iron and optionally 100-500 ppm carbon and / or 50 to 200 ppm zirconium as the balance.
  • the alloy according to the invention is preferably suitable for components which are exposed to oxidizing and corrosive effects at high temperatures and low mechanical loads.
  • Such components can be used to guide a hot gas flow with particular advantage and can be designed, for example, as the inner lining of a combustion chamber, in particular for a gas turbine.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Powder Metallurgy (AREA)
  • Physical Vapour Deposition (AREA)
EP94100485A 1993-02-05 1994-01-14 Alliage résistant à l'oxydation et à la corrosion, à base l'aluminiure de fer dopé et application de cet alliage Expired - Lifetime EP0609682B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4303316 1993-02-05
DE4303316A DE4303316A1 (de) 1993-02-05 1993-02-05 Oxidations- und korrosionsbeständige Legierung auf der Basis von dotiertem Eisenaluminid und Verwendung dieser Legierung

Publications (2)

Publication Number Publication Date
EP0609682A1 true EP0609682A1 (fr) 1994-08-10
EP0609682B1 EP0609682B1 (fr) 2001-03-28

Family

ID=6479708

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94100485A Expired - Lifetime EP0609682B1 (fr) 1993-02-05 1994-01-14 Alliage résistant à l'oxydation et à la corrosion, à base l'aluminiure de fer dopé et application de cet alliage

Country Status (5)

Country Link
US (1) US5422070A (fr)
EP (1) EP0609682B1 (fr)
JP (1) JP3420815B2 (fr)
AT (1) ATE200111T1 (fr)
DE (2) DE4303316A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997028289A1 (fr) * 1996-02-01 1997-08-07 Castolin S.A. Materiau de pulverisation a base de fer pour produire un revetement anticorrosion, procede de production de ce revetement et utilisation de la couche

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6436163B1 (en) * 1994-05-23 2002-08-20 Pall Corporation Metal filter for high temperature applications
DE19634524A1 (de) * 1996-08-27 1998-04-09 Krupp Ag Hoesch Krupp Leichtbaustahl und seine Verwendung für Fahrzeugteile und Fassadenverkleidungen
US6030472A (en) 1997-12-04 2000-02-29 Philip Morris Incorporated Method of manufacturing aluminide sheet by thermomechanical processing of aluminide powders
DE19753876A1 (de) * 1997-12-05 1999-06-10 Asea Brown Boveri Eisenaluminidbeschichtung und Verfahren zum Aufbringen einer Eisenaluminidbeschichtung
DE10332860A1 (de) * 2003-07-18 2005-02-10 Linde Ag Gasbrenner
EP2022294A4 (fr) * 2006-05-30 2014-04-16 Howmet Corp Procede de fusion utilisant un recipient de fusion en graphite
FI126955B (en) * 2013-12-11 2017-08-31 Waertsilae Finland Oy FE-based composition, precursor component and process for producing precursor component

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2768915A (en) * 1954-11-12 1956-10-30 Edward A Gaughler Ferritic alloys and methods of making and fabricating same
WO1990010722A1 (fr) * 1989-03-07 1990-09-20 Martin Marietta Energy Systems, Inc. Alliages de ferrure d'aluminium ayant des proprietes ameliorees pour des applications a temperatures elevees
EP0465686A1 (fr) * 1990-07-07 1992-01-15 Asea Brown Boveri Ag Alliage résistant à l'oxydation et à la corrosion pour pièces utilisables à des températures intermédiaires et basés sur le trialuminiure de fer (Fe3Al) dopé
US5084109A (en) * 1990-07-02 1992-01-28 Martin Marietta Energy Systems, Inc. Ordered iron aluminide alloys having an improved room-temperature ductility and method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856513A (en) * 1972-12-26 1974-12-24 Allied Chem Novel amorphous metals and amorphous metal articles
US4439236A (en) * 1979-03-23 1984-03-27 Allied Corporation Complex boride particle containing alloys
US4365994A (en) * 1979-03-23 1982-12-28 Allied Corporation Complex boride particle containing alloys
US4576653A (en) * 1979-03-23 1986-03-18 Allied Corporation Method of making complex boride particle containing alloys
US4844865A (en) * 1986-12-02 1989-07-04 Nippon Steel Corporation Seawater-corrosion-resistant non-magnetic steel materials
EP0413029B1 (fr) * 1988-12-29 1995-09-20 Matsushita Electric Industrial Co., Ltd. Procede de production d'alliage a occlusion d'hydrogene et electrode utilisant un tel alliage

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2768915A (en) * 1954-11-12 1956-10-30 Edward A Gaughler Ferritic alloys and methods of making and fabricating same
WO1990010722A1 (fr) * 1989-03-07 1990-09-20 Martin Marietta Energy Systems, Inc. Alliages de ferrure d'aluminium ayant des proprietes ameliorees pour des applications a temperatures elevees
US5084109A (en) * 1990-07-02 1992-01-28 Martin Marietta Energy Systems, Inc. Ordered iron aluminide alloys having an improved room-temperature ductility and method thereof
EP0465686A1 (fr) * 1990-07-07 1992-01-15 Asea Brown Boveri Ag Alliage résistant à l'oxydation et à la corrosion pour pièces utilisables à des températures intermédiaires et basés sur le trialuminiure de fer (Fe3Al) dopé
US5158744A (en) * 1990-07-07 1992-10-27 Asea Brown Boveri Ltd. Oxidation- and corrosion-resistant alloy for components for a medium temperature range based on doped iron aluminide, Fe3 Al

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997028289A1 (fr) * 1996-02-01 1997-08-07 Castolin S.A. Materiau de pulverisation a base de fer pour produire un revetement anticorrosion, procede de production de ce revetement et utilisation de la couche

Also Published As

Publication number Publication date
DE59409701D1 (de) 2001-05-03
EP0609682B1 (fr) 2001-03-28
JP3420815B2 (ja) 2003-06-30
US5422070A (en) 1995-06-06
ATE200111T1 (de) 2001-04-15
JPH06240415A (ja) 1994-08-30
DE4303316A1 (de) 1994-08-11

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