EP0256555B1 - Alliages renforcés par dispersion - Google Patents

Alliages renforcés par dispersion Download PDF

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Publication number
EP0256555B1
EP0256555B1 EP87111982A EP87111982A EP0256555B1 EP 0256555 B1 EP0256555 B1 EP 0256555B1 EP 87111982 A EP87111982 A EP 87111982A EP 87111982 A EP87111982 A EP 87111982A EP 0256555 B1 EP0256555 B1 EP 0256555B1
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EP
European Patent Office
Prior art keywords
alloy
chromium
aluminum
volume
product according
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
EP87111982A
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German (de)
English (en)
Other versions
EP0256555A3 (en
EP0256555A2 (fr
Inventor
Raymond Christopher Benn
John Joseph Fischer
Gaylord Darrell Smith
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Huntington Alloys Corp
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Inco Alloys International Inc
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Publication date
Application filed by Inco Alloys International Inc filed Critical Inco Alloys International Inc
Priority to AT87111982T priority Critical patent/ATE81679T1/de
Publication of EP0256555A2 publication Critical patent/EP0256555A2/fr
Publication of EP0256555A3 publication Critical patent/EP0256555A3/en
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Publication of EP0256555B1 publication Critical patent/EP0256555B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0292—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with more than 5% preformed carbides, nitrides or borides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1084—Alloys containing non-metals by mechanical alloying (blending, milling)
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0026—Matrix based on Ni, Co, Cr or alloys thereof

Definitions

  • the present invention is directed to dispersion-strengthened (DS) alloys, and more particularly to oxide-dispersion strengthened (ODS) iron-base alloys which manifest an exceptional degree of resistance to oxidation at temperatures as high as 1300°C (approx. 2400°F) whereby the alloys are useful in the production of advanced aircraft gas turbine engine components and in demanding industrial applications.
  • DS dispersion-strengthened
  • ODS oxide-dispersion strengthened
  • the '161 ODS material (commercially containing about 20% chromium, 4.5% aluminum) exhibits good corrosion and oxidation resistance at, say, up to 1200°C, it is prone to undergo premature slagging attack (formation of low melting point phases/compounds through a chemical reaction with corrosive deposits from and/or the environment per se) and/or accelerated attack upon exposure at higher temperatures after short intervals of time, the failure being of the catastrophic type.
  • accelerated oxidation may be considered as the rapid mass change of an alloy by oxidation. The mass change is virtually always dramatically positive if all the oxide is collected and weighed. In undergoing the ravages occasioned by such attack the alloy surface converts to friable iron oxide and iron-chromium spinels.
  • burner cans in aircraft gas turbine engines of advanced design are currently intended for use at increasingly higher operating temperatures, i.e., about 1250°C (2308°F), and above, e.g., 1300°C (2372°F).
  • operating temperatures i.e., about 1250°C (2308°F)
  • above e.g., 1300°C (2372°F)
  • industrial applications involving intimate contact with such aggressive corrosives as flue dust, fly ash, molten glass, etc. require more oxidation and/or corrosion-resistant materials.
  • Kornilov "Aluminum in Iron and Steel” by S.C. Case and K.R. Van Horn, John Wiley and Sons (1953). Kornilov studied the effect of up to 10% aluminum and up to 65% chromium on scaling losses in both cast and wrought Fe-Cr-Al alloys. Aluminum benefited scaling resistance but seemingly there was little benefit conferred by chromium beyond the 25% level at 1100-1400°C. None in the Kornilov investigation involved fabricability of an ODS product or manufacture of sheet.
  • alloys exhibiting high resistance to oxidation at temperatures as high as 1300°C have the compositions set forth in claim 1.
  • the present invention contemplates dispersion strengthened powder metallurgically produced iron-chromium-aluminum alloys containing from 20 to 30% chromium, e.g. at least 22.5% Cr, and 5 to 8% aluminum.
  • the aluminum content should not exceed 6.25% i.e. the aluminum should be from 5% to 6.25%.
  • the chromium should be from 23 to 27% and the aluminum from 5 to 6%.
  • the alloys may also contain up to 5% titanium, up to 2% each of zirconium, hafnium, tantalum and venadium, up to 6% each of molybdenum and tungsten, up to 0.5% each of silicon and niobium, up to 0.05% each of calcium, yttrium and rare earth metals, up to 0.2% boron and the balance, apart from impurities, iron plus, to enhance strength, a small but effective amount, e.g., 0.2 volume %, of at least one finely divided dispersoid having a melting point of at least about 1510°C (2750°F) and selected from the group consisting of oxides, nitrides, carbides, borides and other refractory materials.
  • oxides may be present up to about 10 volume % whereas carbides should not exceed about 2 volume %.
  • Nitrides and borides need not exceed 5% by volume.
  • the chromium content should not exceed 30% to minimize the formation of deleterious levels of topologically close packed (TCP) phases such as sigma, phases which adversely impact mechanical properties.
  • TCP topologically close packed
  • Aluminum should be from 5% to 8% for oxidation and corrosion resistance but as indicated, supra, preferably should not exceed 6% when seeking the optimum in terms of fabrication into sheet, strip, etc.
  • Such elements as nickel and cobalt are not required and confer no particular advantage.
  • Carbon need not exceed 0.1% though higher percentages can be tolerated.
  • Our investigation has not shown silicon or boron to be particularly beneficial. Boron is thought to be causative of (or a contributor to) distortion when the sheet product form is heat treated at elevated temperatures. It preferably should not exceed 0.1%.
  • Such constituents as titanium, zirconium, tantalum, niobium, hafnium, zirconium and vanadium need not exceed 1%.
  • Tantalum for example, at the 1% level has resulted in a loss of fabricability. It tends to stiffen the alloys of the invention and possibly raises the ductile-brittle trans-formation temperature too much.
  • a range of titanium from 0.2 or 0.25 to 0.75% is preferred.
  • the alloys of the invention are most preferably produced by mechanical alloying as described in U.S. 3,992,161, although other dispersoid strengthening powder metallurgy processes may be employed.
  • a series of alloy compositions were prepared using raw material powders namely, elemental (e.g., Fe, Cr, Al), master alloy (e.g., Fe-Cr-Al-Ti) and yttrium bearing oxide (Y2O3) which powders were thereafter blended to produce the chemistries given in Table I, in which Alloys H and I are in accordance with the invention but the others are not.
  • the powder blends were mechanically alloyed (MA) in high energy ball mills under an argon atmosphere for about 24 hours at a ball-to-powder ratio of about 20:1 using steel balls as the impacting/grinding media.
  • the MA powders were screened to remove the coarser particles (above about 600 microns), placed in mild steel cans, sealed and hot compacted by extrusion.
  • the extrusions were decanned and then hot and cold rolled to 1.25 mm (0.05in) thick sheet, the sheet thereafter being subjected to a final anneal which was typically 1315°C (2400°F) for 1 hour to achieve recrystallization.
  • Alloys B, and C are representative of a typical '161 composition, i.e., 20% Cr/4.5% Al. At 1300°C, the initiation of accelerated oxidation to the point of completion spanned but 2 days. See Table III. Increasing the chromium content to 24% reduced in half the rate of accelerated oxidation (Alloy D, Table III) and increasing the aluminum level from 4.5 to 6.5% to give an alloy in accordance with the invention again markedly reduced the rate of attack (Alloy H, Table III). This pattern of behavior is of practical importance because a significant reduction in the rate of attack may extend service life to allow a repair operation and, thus, avoid the consequences of a catastrophic failure.
  • Figures 1-3 illustrate more graphically what happens by increasing the chromium level of a typical commercial '161 alloy which contained, apart from the different chromium levels, 0.02%/wt C, 4.5%/wt Al, 0.3%/wt. Ti, 0.5%/vol. Y2O3, incidental impurities, with iron being essentially the balance.
  • the spallation rate mass change
  • the aluminum content should also be increased, preferably proportionately, to reduce the rate of spallation and ensure better integrity of the alloy composition. This is reflected by Figures 4 and 5 where at a 25% Cr level the spallation rate is markedly reduced through the co-presence of an additional 2% of aluminum above the '161 alloy.
  • a further practical advantage of the alloys of our invention is that they are deemed to afford improved high temperature oxidation and corrosion resistance in thin gauges in comparison with prior art material.
  • Sheet thickness for example, of 1.25 mm (0.05 in.) are typical for the 20% Cr/4.5% Al '161 alloy as commercially produced.
  • In such gauge section there is a propensity to undergo accelerated oxidation attack early on for lack of, comparatively speaking, bulk concentration of aluminum and chromium atoms available for surface (oxide) protection. Put another way, such accelerated attack can cause pitting, pitting which will penetrate through, for example, sheet. Alloys of the invention offer a higher concentration of reserve aluminum and/or chromium atoms.
  • FIG. 6 depicts a general correlation between chromium and aluminum in respect of their combinative effect on bendability, a criterion used to assess fabricability.
  • sheet specimens approximately 1.3 mm (0.05 in) (1 t) thick, 1.27 mm (1/2 in) in width and about 5-10 cm (2 to 4 in) in length were bent over a rod of approximately 1.6 mm (0.1 in) thick (2 t).
  • Tests were made in both the longitudinal and transverse directions. The black shaded area is indicative that some cracking was evident from the tests.
  • the standard '161 alloy of 20% Cr/4.5% Al is quite fabricable. But at a 30% Cr/4.5% Al level cracking was experienced.
  • alloys contemplated herein can be used in hot worked and/or machined bar and other mill product shaped forms including forgings and tubing. It may be cost effective, for example, to machine components from bar for, say, flame guides or glass extrusion dies.

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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)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Colloid Chemistry (AREA)

Claims (11)

  1. Un alliage en poudre fer-chrome-aluminium renforcé par dispersion produit par métallurgie présentant une résistance élevée à l'oxydation à des températures pouvant aller jusqu'à 1300°C et consistant en de 20 à 30% en poids de chrome, de 5 à 8% en poids d'aluminium, une quantité allant de 0,2% à 10% en volume d'un système colloïdal à grande dispersion réfractaire efficace pour accroître la solidité et choisi dans le groupe consistant en les oxydes, les nitrures, les carbures et les borures, avec ou sans un ou plusieurs des constituants supplémentaires suivants : jusqu'à 5% en poids de titane, jusqu'à 2% en poids chacun de zirconium, d'hafnium, de tantale et de vanadium, jusqu'à 6% en poids chacun de molybdène et de tungstène, jusqu'à 0,5% en poids de silice, jusqu'à 0,5% en poids de niobium, jusqu'à 0,05% en poids chacun de calcium, d'yttrium et de métaux terreux rares, jusqu'à 0,2% en poids de bore et le restant, exception faite des impuretés, étant du fer.
  2. Un alliage selon la revendication 1 contenant au moins 22,5% de chrome.
  3. Un alliage selon la revendication 1 ou la revendication 2 contenant de 0,25 à 0,75% de titane.
  4. Un alliage en poudre fer-chrome-aluminium renforcés par dispersion produit par métallurgie sous la forme d'un produit laminé à plat tel qu'une feuille et une bande caractérisé par une bonne fabricabilité et résistance à l'oxydation à des températures allant jusqu'à 1300°C, ledit produit étant formé à partir d'un alliage selon l'une quelconque des revendications précédentes dans lequel la teneur en chrome est d'au moins 23% en poids et la teneur en aluminium va de 5 à 6,25% en poids.
  5. Un produit en alliage selon la revendication 4 dans lequel le titane est présent en une quantité qui va de 0,2 à 0,75% en poids.
  6. Un produit en alliage selon la revendication 4 ou la revendication 5 dans lequel la teneur en aluminium ne dépasse pas 6% en poids.
  7. Un produit en alliage selon l'une quelconque des revendications 4 à 6 dans lequel la teneur en chrome va de 23 à 27% en poids.
  8. Un produit en alliage selon l'une quelconque des revendications 4 à 7 dans lequel le système colloïdal à grande dispersion réfractaire est un ou plusieurs oxydes en une quantité allant jusqu'à 10% en volume, carbures jusqu'à 2% en volume, nitrures jusqu'à 5% en volume et borures jusqu'à 5% en volume, tous les pourcentages étant par rapport au volume total de l'alliage.
  9. Un composant métallique pour la section de l'étape chaude d'un moteur d'avion à turbine à gaz, formé à partir d'un produit en alliage selon l'une quelconque des revendications 4 à 8.
  10. Un composant métallique selon la revendication 9 sous la forme d'un brûleur.
  11. Un produit en alliage selon l'une quelconque des revendications 4 à 9 dans lequel la poudre est produite par alliage mécanique.
EP87111982A 1986-08-18 1987-08-18 Alliages renforcés par dispersion Expired - Lifetime EP0256555B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87111982T ATE81679T1 (de) 1986-08-18 1987-08-18 Dispersionsverstaerkte legierungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US89774586A 1986-08-18 1986-08-18
US897745 1986-08-18

Publications (3)

Publication Number Publication Date
EP0256555A2 EP0256555A2 (fr) 1988-02-24
EP0256555A3 EP0256555A3 (en) 1989-02-22
EP0256555B1 true EP0256555B1 (fr) 1992-10-21

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EP87111982A Expired - Lifetime EP0256555B1 (fr) 1986-08-18 1987-08-18 Alliages renforcés par dispersion

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EP (1) EP0256555B1 (fr)
JP (1) JP2845877B2 (fr)
AT (1) ATE81679T1 (fr)
AU (1) AU600009B2 (fr)
DE (1) DE3782294T2 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04194038A (ja) * 1990-11-27 1992-07-14 Gunze Ltd 紡績糸の製造方法
US5427601A (en) * 1990-11-29 1995-06-27 Ngk Insulators, Ltd. Sintered metal bodies and manufacturing method therefor
US5167728A (en) * 1991-04-24 1992-12-01 Inco Alloys International, Inc. Controlled grain size for ods iron-base alloys
JP2585900B2 (ja) * 1991-08-28 1997-02-26 株式会社日立製作所 耐熱性強化部材の製造方法
GB9206548D0 (en) * 1992-03-26 1992-05-06 British Ceramic Service Co Improvements in or relating to kilns
DE19511089A1 (de) * 1995-03-25 1996-09-26 Plansee Metallwerk Bauteil mit aufgelöteten Folien aus ODS-Sintereisen-Legierungen
SE520561C2 (sv) * 1998-02-04 2003-07-22 Sandvik Ab Förfarande för framställning av en dispersionshärdande legering
US6416871B1 (en) 1999-05-27 2002-07-09 Sandvik Ab Surface modification of high temperature alloys
DE10261207A1 (de) * 2002-12-20 2004-07-15 Mk Metallfolien Gmbh Eisenlegierung, insbesondere zur Verwendung in einer Abgasreinigungseinheit
CN108330408B (zh) * 2017-01-18 2019-10-01 天津大学 一种高强度含铝铁素体ods钢及其制备方法
CN108950357B (zh) * 2018-07-27 2020-03-27 中南大学 一种多尺度多相弥散强化铁基合金及其制备和表征方法
CN110343935B (zh) * 2019-07-11 2021-02-09 中国科学院金属研究所 采用表面氧化+爆炸压实制备氧化物弥散强化铁素体钢

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE794142A (fr) * 1972-01-17 1973-07-17 Int Nickel Ltd Alliages pour hautes temperatures
US3992161A (en) * 1973-01-22 1976-11-16 The International Nickel Company, Inc. Iron-chromium-aluminum alloys with improved high temperature properties
US4391634A (en) * 1982-03-01 1983-07-05 Huntington Alloys, Inc. Weldable oxide dispersion strengthened alloys
US4402746A (en) * 1982-03-31 1983-09-06 Exxon Research And Engineering Co. Alumina-yttria mixed oxides in dispersion strengthened high temperature alloys
US4619699A (en) * 1983-08-17 1986-10-28 Exxon Research And Engineering Co. Composite dispersion strengthened composite metal powders
JPS61221303A (ja) * 1985-03-27 1986-10-01 Riken Corp 酸化物分散Ｆｅ基高合金の製造方法

Also Published As

Publication number Publication date
AU600009B2 (en) 1990-08-02
AU7672387A (en) 1988-02-25
JPS6350448A (ja) 1988-03-03
DE3782294D1 (de) 1992-11-26
EP0256555A3 (en) 1989-02-22
EP0256555A2 (fr) 1988-02-24
DE3782294T2 (de) 1993-03-04
JP2845877B2 (ja) 1999-01-13
ATE81679T1 (de) 1992-11-15

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