EP0609682B1 - 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
EP0609682B1
EP0609682B1 EP94100485A EP94100485A EP0609682B1 EP 0609682 B1 EP0609682 B1 EP 0609682B1 EP 94100485 A EP94100485 A EP 94100485A EP 94100485 A EP94100485 A EP 94100485A EP 0609682 B1 EP0609682 B1 EP 0609682B1
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EP
European Patent Office
Prior art keywords
alloy
oxidation
corrosion
boron
iron
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.)
Expired - Lifetime
Application number
EP94100485A
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German (de)
English (en)
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EP0609682A1 (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 Schweiz AG
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Publication date
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Publication of EP0609682A1 publication Critical patent/EP0609682A1/fr
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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 Fe 3 Al can be used in parts of thermal machines that are subjected to high thermal stress 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 after the introductory part of Claim 1.
  • an oxidation and corrosion-resistant alloy after the introductory part of Claim 1.
  • a known alloy contains 24 to 28 at% as components 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 stands out in the temperature range between 300 and 700 ° C due to its high resistance to oxidation and corrosion as well as sufficient heat resistance. At At room temperature, this alloy also has one for many Applications sufficient ductility.
  • the invention as set out in claim 1 lies based on the task of an alloy based on to develop doped iron aluminide, which is characterized by a high resistance to oxidation and corrosion Temperatures above 700 ° C.
  • 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 constituents exclusively contain metals which are comparatively inexpensive and are available independently of strategic and political influence.
  • the alloy according to the invention moreover has a comparatively low density of only 6.5 g / cm 3 for certain applications in thermal turbomachines with sufficient strength and ductility.
  • the only figure shows a diagram in which the Oxidation and corrosion behavior of an alloy I according to Invention and three alloys II, III and IV according to the state the technology at 1200 ° C as a function of time is.
  • Alloy II (under the trademark "Incoloy” and the name MA 956 commercially available, oxidation and corrosion-resistant alloy with good properties at high temperatures): 20% by weight chromium, 4.5% by weight aluminum, 0.5% by weight titanium, 0.5 wt% yttrium oxide Y 2 O 3 , balance iron
  • Alloy IV (under the trademark "Hastelloy” and the Designation X commercially available, oxidation and corrosion-resistant alloy with good properties high temperatures): 22% by weight chromium, 18.5% by weight Fe, 1.5% by weight cobalt, 9% by weight molybdenum, 0.6% by weight tungsten, 0.5% by weight manganese, 0.5% by weight silicon, 0.1% by weight Carbon, balance nickel
  • Alloys I and III and an alloy which has the constituents specified for alloy I as well as 300 ppm C and 100 ppm Zr were melted in an arc furnace under argon as a protective gas.
  • 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.
  • Test specimens for tensile tests and platelets with a surface area of a few cm 2 and a thickness of approximately 1-2 mm were produced from this and from alloys II and IV.
  • 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 mass loss - ⁇ W [mg] or the mass increase ⁇ W [mg], based on the size of the surface A 0 [cm 2 ] of each of the platelets, is then a measure of the oxidation and corrosion resistance of alloys I to IV.
  • the oxidation and corrosion behavior of the alloys I to IV simulated by the quotient ⁇ W / A 0 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 is even with an alloy designed according to the invention, which has the same components as alloy I, but additionally 300 ppm carbon and 100 ppm zirconium contains. This alloy stands out additionally by slightly increased strength and improved Weldability.
  • the aluminum content is at least 24 and at most 28 at%. Sinks Aluminum content below 24 at%, so the deteriorates Resistance to oxidation and corrosion of the inventive Alloy. If the aluminum content is greater than 28 at%, so the alloy becomes increasingly brittle.
  • the hardness and the Strength of the alloy according to the invention increased.
  • the Elasticity elongation at break
  • too Tungsten and / or tantalum with a share of 0.1 to 2 at% be alloyed.
  • a proportion of 0.1 to 2 at% silicon improves the Castability of the alloy according to the invention and acts favorable for their 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 TiB 2 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 below 0.1 at% and that of titanium below 0.01 at%, the oxidation and corrosion resistance of the alloy according to the invention deteriorates 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 rest.
  • the alloy according to the invention is preferred for components suitable, which at high temperatures and low mechanical loads oxidizing and corrosive Effects are exposed.
  • Such components can with serve a particular advantage of guiding a hot gas flow and approximately 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)

Claims (6)

  1. Alliage résistant à l'oxydation et à la corrosion à base d'aluminiure de fer dopé qui, outre le fer et l'aluminium, comporte comme autres composants d'alliage au moins du niobium, du chrome, du silicium et du bore, caractérisé en ce qu'il contient les composants d'alliage suivants en pourcentages atomiques:
    24 - 28 aluminium
    0,1 - 2 niobium, tantale et/ou tungstène
    0,1 - 10 chrome
    0,1 - 2 silicium
    0,1 - 5 bore
    0,1 - 2 titane
    optionnellement
       100 - 500 ppm carbone et/ou 50 - 200 ppm zirconium
       reste fer.
  2. Alliage suivant la revendication 1, caractérisé en ce qu'il contient plus de 1% atomique, mais au maximum 5% atomiques, de bore.
  3. Alliage suivant l'une quelconque des revendications 1 ou 2, caractérisé en ce qu'il contient les composants d'alliage suivants:
    26 - 28 aluminium
    0,5 - 1,5 niobium
    3 - 7 chrome
    0,5 - 1,5 silicium
    2 - 4 bore
    0,5 - 1,5 titane
       reste fer.
  4. Application de l'alliage suivant la revendication 1 pour un élément de construction exposé à des effets oxydants et/ou corrosifs à des températures élevées et sous une charge mécanique faible.
  5. Application suivant la revendication 4, caractérisée en ce que l'élément de construction sert à la conduite d'un courant de gaz très chauds.
  6. Application suivant la revendication 5, caractérisée en ce que l'élément de construction constitue le revêtement intérieur d'une chambre de combustion, en particulier pour une turbine à gaz.
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 EP0609682A1 (fr) 1994-08-10
EP0609682B1 true EP0609682B1 (fr) 2001-03-28

Family

ID=6479708

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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)

Families Citing this family (8)

* 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
DE19603515C1 (de) * 1996-02-01 1996-12-12 Castolin Sa Spritzwerkstoff auf Eisenbasis zum Herstellen einer korrosionsbeständigen Beschichtung, Herstellungsverfahren für die Beschichtung sowie Verwendung der Schicht
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

Family Cites Families (10)

* 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
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
DE68924346T2 (de) * 1988-12-29 1996-05-15 Matsushita Electric Ind Co Ltd Verfahren zur herstellung einer legierung mit wasserstoffeinlagerung und elektrode aus einer derartigen legierung.
US4961903A (en) * 1989-03-07 1990-10-09 Martin Marietta Energy Systems, Inc. Iron aluminide alloys with improved properties for high temperature applications
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
DE59007276D1 (de) * 1990-07-07 1994-10-27 Asea Brown Boveri Oxydations- und korrosionsbeständige Legierung für Bauteile für einen mittleren Temperaturbereich auf der Basis von dotiertem Eisenaluminid Fe3Al.

Also Published As

Publication number Publication date
ATE200111T1 (de) 2001-04-15
DE59409701D1 (de) 2001-05-03
JP3420815B2 (ja) 2003-06-30
US5422070A (en) 1995-06-06
JPH06240415A (ja) 1994-08-30
EP0609682A1 (fr) 1994-08-10
DE4303316A1 (de) 1994-08-11

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