EP0143727A2 - Aluminium-based alloys having a high heat stability - Google Patents

Aluminium-based alloys having a high heat stability Download PDF

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EP0143727A2
EP0143727A2 EP84420198A EP84420198A EP0143727A2 EP 0143727 A2 EP0143727 A2 EP 0143727A2 EP 84420198 A EP84420198 A EP 84420198A EP 84420198 A EP84420198 A EP 84420198A EP 0143727 A2 EP0143727 A2 EP 0143727A2
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alloy according
weight
alloy
alloys
solidification
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German (de)
French (fr)
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EP0143727A3 (en
EP0143727B1 (en
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Salim Dermarkar
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Cegedur Societe de Transformation de lAluminium Pechiney SA
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Cegedur Societe de Transformation de lAluminium Pechiney SA
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/08—Amorphous alloys with aluminium as the major constituent

Definitions

  • the invention relates to Al-based alloys with high heat stability.
  • Alloys based on A1 are known which exhibit good hot stability, in particular those described in French patent application FR 2 190 553 or US patent 4 347 076.
  • alloys based are described. of Al containing from 3 to 15% (by weight) of transition element belonging to the group Ti, V, Cr, Mn, Co, Ni, Fe, Zr, Nb and Mo. However, these only retain a hardness lower than 190 Vickers units, for periods of maintenance of 1 week at temperatures lower than or equal to 400 ° C.
  • the invention relates to Al alloys whose heat stability is significantly higher.
  • the alloys according to the invention contain, in addition to the Al and the inevitable processing impurities, at least 5 to 20% (by weight) of Fe, and more than 0.05% Ni and 0.5% Mo.
  • the sum of the Ni + Mo contents must not exceed 8%, so as not to exceed the retention capacity of the alloying elements during rapid solidification (> 10 4 ° C / second) of the alloy.
  • the% Mo /% Ni ratio must be greater than 0.5 to obtain the desired hot stability. This stability is very much greater than that which a separate addition of Ni or Mo could confer; this point will be illustrated by examples.
  • One (or more) other refractory element (s) from the group Mn, Si, Cr, Ti, Hf, Zr, Nb, V, W can be added to this basic composition, for a lower overall content. at 5% by weight.
  • the alloys of preferred compositions comprise individually or in combination of 5 to 10% Fe, a ratio and / or a Mo content ⁇ 1%
  • These alloys obtained by rapid solidification (> 10 4 ° C / second), by any known means, present in the solid state of solidification either a single-phase structure (supersaturated solid solution based on Al) or a particular structure made up of this solid solution based on A1 and a fine precipitation of eutectoid type, of a phase (which we will call u) of filiform appearance whose width, on micrographic section, is of the order of 5 to 50 nm
  • This phase contains at least 1 Z by weight of Ni and 1% of Mo.
  • This microcrystalline ⁇ phase has the following interreticular distances: 0.38 - 0.203 to 0.211 - 0.147 - 0.125 - 0.107 nm its structure is probably cubic complex.
  • the size of the crystallites of this phase ⁇ is of the order of 1 nm, which results in the existence of several broad and diffuse rings on the electron diffraction radiographs.
  • the alloys were produced in the form of a ribbon 1 to 5 mm ⁇ 20 to 40 ⁇ m, by rapid solidification on a steel casting wheel, driven at a tangential speed of 45 m / second.
  • alloys 2, 7, 8 which are outside the scope of the invention have poor heat stability, relative to the other alloys according to the invention.
  • a minimum quantity of nickel (and of Mo) is essential to obtain the good properties of heat resistance: the preferred compositions (4, 5, 6 ) have optimal hot characteristics.
  • Table III gives the characteristics of hot resistance for longer-lasting holdings of the alloys (4 to 6) at 400 ° C.
  • the alloy 4 has a precipitation in semi-coherent platelets while in the alloy 8, the precipitation already consists of incoherent globules of Al FeNi type phase. .
  • the thermal stability of alloy 4 is associated with the slower decomposition kinetics observed on this alloy.
  • the alloys according to the invention can be used for parts of turbomachines operating at temperatures below 350 ° C for fairly long periods or operating at higher temperature for fairly short periods (missile bodies).
  • They can also be used in the form of coatings on substrates of different nature, and, optionally hardened by laser treatment or electronic bombardment.

Abstract

1. An Al-based alloy characterised in that it contains (in percent by weight) : 5 =< Fe =< 20 Ni >= 0.05 Mo >= 0.5 with Mo + Ni =< 8 Mo/Ni >= 0.5 and optionally up to 5% in total of one (or more) element(s) from the group Si, Mn, Ti, Hf, Zr, V and Nb, the remainder being Al and inevitable impurities.

Description

L'invention concerne des alliages à base d"Al présentant une grande stabilité à chaud.The invention relates to Al-based alloys with high heat stability.

On connaît des alliages à base d'A1 qui présentent une bonne stabilité à chaud, en particulier ceux décrits dans la demande de brevet français FR 2 190 553 ou le brevet US 4 347 076. Dans la demande française, sont décrits des alliages à base d'Al contenant de 3 à 15 % (en poids) d'élément de transition appartenant au groupe Ti, V, Cr, Mn, Co, Ni, Fe, Zr, Nb et Mo. Cependant, ceux-ci ne conservent qu'une dureté inférieure à 190 unités Vickers, pour des durées de maintien de 1 semaine à des températures inférieures ou égales à 400° C.Alloys based on A1 are known which exhibit good hot stability, in particular those described in French patent application FR 2 190 553 or US patent 4 347 076. In the French application, alloys based are described. of Al containing from 3 to 15% (by weight) of transition element belonging to the group Ti, V, Cr, Mn, Co, Ni, Fe, Zr, Nb and Mo. However, these only retain a hardness lower than 190 Vickers units, for periods of maintenance of 1 week at temperatures lower than or equal to 400 ° C.

Dans le brevet US 4 347 076 sont décrits des alliages à base d'Al contenant de 5 à 16 % (en poids) d'éléments de transition du groupe Fe, Cr, Ni, Co, Mn, V, Ti, Zr, Mo, W et B avec Mn+V+Ti+Zr+hIo+W ≤ 5 % et B ≤ 1 %. Ces alliages n'atteignent que des duretés inférieures à 240 unités Vickers après un traitement de 1 h 30 mn à 400° C.In US patent 4 347 076 are described alloys based on Al containing from 5 to 16% (by weight) of transition elements from the group Fe, Cr, Ni, Co, Mn, V, Ti, Zr, Mo , W and B with Mn + V + Ti + Zr + hIo + W ≤ 5% and B ≤ 1%. These alloys only reach hardnesses lower than 240 Vickers units after a treatment of 1 h 30 min at 400 ° C.

L'invention concerne des alliages d'Al dont la stabilité à chaud est notablement supérieure. Les alliages selon l'invention contiennent, outre l'Al et les impuretés d'élaboration inévitables, au moins de 5 à 20 % (en poids) de Fe, et plus de 0,05 % Ni et 0,5 % Mo.The invention relates to Al alloys whose heat stability is significantly higher. The alloys according to the invention contain, in addition to the Al and the inevitable processing impurities, at least 5 to 20% (by weight) of Fe, and more than 0.05% Ni and 0.5% Mo.

Il a été trouvé que la somme des teneurs en Ni+Mo ne doit pas excéder 8 %, de manière à ne pas dépasser la capacité de rétention des éléments d'alliages lors d'une solidification rapide (> 104 °C/seconde) de l'alliage. De plus, le rapport % Mo/% Ni doit être supérieur à 0,5 pour obtenir la stabilité à chaud désirée. Cette stabilité est très largement supérieure à celle que pourrait conférer une addition séparée de Ni ou de Mo ; ce point sera illustré par des exemples.It has been found that the sum of the Ni + Mo contents must not exceed 8%, so as not to exceed the retention capacity of the alloying elements during rapid solidification (> 10 4 ° C / second) of the alloy. In addition, the% Mo /% Ni ratio must be greater than 0.5 to obtain the desired hot stability. This stability is very much greater than that which a separate addition of Ni or Mo could confer; this point will be illustrated by examples.

On peut ajouter à cette composition de base un (ou plusieurs) autre(s) élément(s) réfractaire(s) du groupe Mn, Si, Cr, Ti, Hf, Zr, Nb, V, W, pour une teneur globale inférieure à 5 % en poids.One (or more) other refractory element (s) from the group Mn, Si, Cr, Ti, Hf, Zr, Nb, V, W can be added to this basic composition, for a lower overall content. at 5% by weight.

Les alliages de compositions préférentielles comportent individuellement ou en combinaison de 5 à 10 % Fe, un rapport

Figure imgb0001
et/ou une teneur en Mo ≥ 1%The alloys of preferred compositions comprise individually or in combination of 5 to 10% Fe, a ratio
Figure imgb0001
 and / or a Mo content ≥ 1%

Ces alliages obtenus par solidification rapide (> 104 °C/seconde), par tout moyen connu, présentent à l'état brut de solidification soit une structure monophasée (solution solide sursaturée à base d'Al) soit une structure particulière constituée de cette solution solide à base d'A1 et d'une fine précipitation de type eutectoide, d'une phase (que nous appelerons u) d'aspect filiforme dont la largeur, sur coupe micrographique, est de l'ordre de 5 à 50 nm Cette phase contient au moins 1 Z en poids de Ni et 1 % de Mo. Cette phase µ microcristalline possède les distances interréticulaires suivantes :
0,38 - 0,203 à 0,211 - 0,147 - 0,125 - 0,107 nm sa structure étant probablement cubique complexe. La taille des cristallites de cette phase µ est de l'ordre de 1 nm ce qui se traduit par l'existence de plusieurs anneaux larges et diffus sur les clichés de diffraction électronique.These alloys obtained by rapid solidification (> 10 4 ° C / second), by any known means, present in the solid state of solidification either a single-phase structure (supersaturated solid solution based on Al) or a particular structure made up of this solid solution based on A1 and a fine precipitation of eutectoid type, of a phase (which we will call u) of filiform appearance whose width, on micrographic section, is of the order of 5 to 50 nm This phase contains at least 1 Z by weight of Ni and 1% of Mo. This microcrystalline µ phase has the following interreticular distances:
0.38 - 0.203 to 0.211 - 0.147 - 0.125 - 0.107 nm its structure is probably cubic complex. The size of the crystallites of this phase µ is of the order of 1 nm, which results in the existence of several broad and diffuse rings on the electron diffraction radiographs.

Cette précipitation est particulièrement stable lors des maintiens à chaud, ce qui explique les propriétés ainsi obtenues. Lors de ces maintiens, la phase µ se décompose progressivement en plaquettes semi- cohérentes (phase p') puis en globules incohérents ayant la structure du composé Al9FeNi.This precipitation is particularly stable during heat maintenance, which explains the properties thus obtained. During these maintenance operations, the µ phase is progressively broken down into semi-coherent platelets (p 'phase) then into incoherent globules having the structure of the compound Al 9 FeNi.

L'invention sera mieux comprise à l'aide des exemples suivants et figures suivantes :

  • La figure 1 représente l'évolution de la dureté des alliages après maintien de 10 mn à diverses températures.
  • La figure 2 représente, au grossissement 31000, la microstructure de l'alliage 8 après maintien de 10 mn à 400° C.
  • La figure 3 représente, au grossissement 31000, la microstructure de l'alliage 4 après maintien de 10 mn à 400° C.
The invention will be better understood using the following examples and the following figures:
  • FIG. 1 represents the evolution of the hardness of the alloys after maintaining 10 minutes at various temperatures.
  • FIG. 2 represents, at 31000 magnification, the microstructure of alloy 8 after holding for 10 min at 400 ° C.
  • FIG. 3 represents, at 31000 magnification, the microstructure of alloy 4 after holding for 10 min at 400 ° C.

EXEMPLESEXAMPLES

Les alliages dont les compositions pondérales sont reportées au tableau 1, ont été élaborés sous forme de ruban 1 à 5 mm x 20 à 40 µm, par solidification rapide sur une roue de coulée en acier, animée d'une vitesse tangentielle de 45 m/seconde.The alloys, the weight compositions of which are given in Table 1, were produced in the form of a ribbon 1 to 5 mm × 20 to 40 μm, by rapid solidification on a steel casting wheel, driven at a tangential speed of 45 m / second.

Ces alliages ont été portés 10 mn à différentes températures, entre 300 et 500° C et les mesures de microdureté Vickers sous 10 g ont été effectuées. Les résultats (moyenne de 6 essais) en sont reportés au tableau II et représentés graphiquement sur la figure 1.These alloys were brought 10 minutes at different temperatures, between 300 and 500 ° C. and the Vickers microhardness measurements under 10 g were carried out. The results (average of 6 tests) are reported in Table II and shown graphically in Figure 1.

On peut constater que les alliages 2, 7, 8 qui sont hors du domaine de l'invention présentent une stabilité à chaud médiocre, relativement aux autres alliages conformes à l'invention. De plus, comme le montrent les essais effectués sur l'alliage 7 (et 8), une quantité minimale de nickel (et de Mo) est indispensable pour obtenir les bonnes propriétés de résistance à chaud : les compositions préférentielles (4, 5, 6) présentent les caractéristiques à chaud optimales.It can be seen that the alloys 2, 7, 8 which are outside the scope of the invention have poor heat stability, relative to the other alloys according to the invention. In addition, as shown by the tests carried out on alloy 7 (and 8), a minimum quantity of nickel (and of Mo) is essential to obtain the good properties of heat resistance: the preferred compositions (4, 5, 6 ) have optimal hot characteristics.

Le tableau III donne les caractéristiques de résistance à chaud pour des maintiens de plus longue durée des alliages (4 à 6) à 400° C.Table III gives the characteristics of hot resistance for longer-lasting holdings of the alloys (4 to 6) at 400 ° C.

On remarque que sur les figures 2 et 3, pour une même température de maintien, l'alliage 4 présente une précipitation en plaquettes semi- cohérentes alors que dans l'alliage 8, la précipitation est déjà constituée de globules incohérents de phase type Al FeNi. La stabilité thermique de l'alliage 4 est associée à la cinétique de décomposition plus lente observée sur cet alliage.Note that in FIGS. 2 and 3, for the same holding temperature, the alloy 4 has a precipitation in semi-coherent platelets while in the alloy 8, the precipitation already consists of incoherent globules of Al FeNi type phase. . The thermal stability of alloy 4 is associated with the slower decomposition kinetics observed on this alloy.

Les alliages selon l'invention pourront être utilisés pour des parties de turbomachines fonctionnant à des températures inférieures à 350° C pendant d'assez longues durées ou fonctionnant à température plus élevée pendant des durées assez courtes (corps de missiles).The alloys according to the invention can be used for parts of turbomachines operating at temperatures below 350 ° C for fairly long periods or operating at higher temperature for fairly short periods (missile bodies).

Ils peuvent également être utilisés sous forme de revêtements sur des substrats de nature différente, et, éventuellement durcis par traitement laser ou bombardement électronique.

Figure imgb0002
Figure imgb0003
Figure imgb0004
 They can also be used in the form of coatings on substrates of different nature, and, optionally hardened by laser treatment or electronic bombardment.
Figure imgb0002
Figure imgb0003
Figure imgb0004

Claims (11)

1°/ Alliage à base d'Al contenant au moins les éléments Fe, Ni, Mo, caractérisé en ce que la composition (en poids %) est la suivante :
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
reste A1 et impuretés inévitables1 ° / Al-based alloy containing at least the elements Fe, Ni, Mo, characterized in that the composition (by weight%) is as follows:
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
 remains A1 and unavoidable impurities 2°/ Alliage selon la revendication 1, caractérisé en ce que
Figure imgb0010
 2 ° / alloy according to claim 1, characterized in that
Figure imgb0010
 3°/ Alliage selon l'une des revendications 1 ou 2, caractérisé en ce que
Figure imgb0011
 3 ° / alloy according to one of claims 1 or 2, characterized in that
Figure imgb0011
 4°/ Alliage selon l'une des revendications 1 à 3, caractérisé en ce que
Figure imgb0012
 4 ° / alloy according to one of claims 1 to 3, characterized in that
Figure imgb0012
 5°/ Alliage selon l'une des revendications 1 à 4, caractérisé en ce qu'il comporte en outre un (ou plusieurs) élément(s) du groupe Si, Mn, Cr, Ti, Hf, Zr, V, W, Nb pour une teneur globale de ces'derniers inférieure à 5 % (en poids).5 ° / alloy according to one of claims 1 to 4, characterized in that it further comprises one (or more) element (s) of the group Si, Mn, Cr, Ti, Hf, Zr, V, W, Nb for an overall content of these latter less than 5% (by weight). 6°/ Alliage selon l'une des revendications 1 à 5, caractérisé en ce qu'à l'état brut de solidification, la structure est une solution solide sursaturée à base d'Al.6 ° / alloy according to one of claims 1 to 5, characterized in that in the raw solidification state, the structure is a supersaturated solid solution based on Al. 7°/ Alliage selon l'une des revendications 1 à 5; caractérisé en ce qu'il comporte à l'état brut de solidification, outre la solution solide, une phase cristalline dont les distances interréticulaires sont :
0,38 - 0,203 à 0,211 - 0,147 - 0,125 - 0,107 nm.7 ° / alloy according to one of claims 1 to 5; characterized in that it comprises in the solid state of solidification, in addition to the solid solution, a crystalline phase whose interreticular distances are:
0.38 - 0.203 to 0.211 - 0.147 - 0.125 - 0.107 nm. 8°/ Alliage selon la revendication 7, caractérisé en ce que la phase cristalline contient au moins 1 % en poids de Ni et 1 % en poids de Mo.8 ° / alloy according to claim 7, characterized in that the crystalline phase contains at least 1% by weight of Ni and 1% by weight of Mo. 9°/ Alliage selon l'une des revendications 7 ou 8, caractérisé en ce qu'à l'état brut de solidification, la grosseur des grains de la phase cristalline est de l'ordre de 1 nm.9 ° / alloy according to one of claims 7 or 8, characterized in that in the raw solidification state, the size of the grains of the crystalline phase is of the order of 1 nm. 10°/ Alliage selon la revendication 9, caractérisé en ce que la phase microcristalline forme un réseau filiforme dont la largeur, sur coupe micrographique, est comprise entre 5 à 50 nm..10 ° / alloy according to claim 9, characterized in that the microcrystalline phase forms a filiform network whose width, on micrographic section, is between 5 to 50 nm. 11°/ Procédé d'obtention d'un alliage suivant l'une des revendication 1 à 10, caractérisé en ce que la vitesse de solidification est supérieure à 104 °C/seconde.11 ° / A method of obtaining an alloy according to one of claims 1 to 10, characterized in that the solidification speed is greater than 10 4 ° C / second.
EP84420198A 1983-11-29 1984-11-27 Aluminium-based alloys having a high heat stability Expired EP0143727B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8319434A FR2555610B1 (en) 1983-11-29 1983-11-29 ALUMINUM ALLOYS HAVING HIGH HOT STABILITY
FR8319434 1983-11-29

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EP0143727A2 true EP0143727A2 (en) 1985-06-05
EP0143727A3 EP0143727A3 (en) 1985-07-10
EP0143727B1 EP0143727B1 (en) 1987-06-24

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JP (1) JPS60215730A (en)
KR (1) KR850004122A (en)
DE (1) DE3464387D1 (en)
ES (1) ES538034A0 (en)
FR (1) FR2555610B1 (en)
IL (1) IL73645A (en)
NO (1) NO162426C (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2584095A1 (en) * 1985-06-28 1987-01-02 Cegedur AL ALLOYS WITH HIGH LI AND SI CONTENT AND METHOD OF MANUFACTURE
EP0218035A1 (en) * 1985-10-02 1987-04-15 Allied Corporation Rapidly solidified aluminum based, silicon containing, alloys for elevated temperature applications
WO1988007592A1 (en) * 1987-03-30 1988-10-06 Allied-Signal Inc. Rapidly solidified aluminum based alloys containing silicon for elevated temperature applications
US4878967A (en) * 1985-10-02 1989-11-07 Allied-Signal Inc. Rapidly solidified aluminum based, silicon containing alloys for elevated temperature applications
US4915748A (en) * 1982-09-03 1990-04-10 Alcan International Aluminum alloys

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60234936A (en) * 1984-05-09 1985-11-21 Sumitomo Light Metal Ind Ltd Formed material with superior strength at high temperature made of material of aluminum alloy solidified by rapid
JPS6148551A (en) * 1984-08-13 1986-03-10 Sumitomo Light Metal Ind Ltd Formed material having superior strength at high temperature made of aluminium alloy material solidified by rapid cooling
JPH01149936A (en) * 1987-12-04 1989-06-13 Honda Motor Co Ltd Heat-resistant al alloy for powder metallurgy

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1195247A (en) * 1956-12-14 1959-11-16 Kaiser Aluminium Chem Corp Aluminum alloys
FR1599990A (en) * 1967-12-30 1970-07-20
US4347076A (en) * 1980-10-03 1982-08-31 Marko Materials, Inc. Aluminum-transition metal alloys made using rapidly solidified powers and method
EP0100287A1 (en) * 1982-07-06 1984-02-08 CNRS, Centre National de la Recherche Scientifique Amorphous or microcrystalline alloys based on aluminium

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1195247A (en) * 1956-12-14 1959-11-16 Kaiser Aluminium Chem Corp Aluminum alloys
FR1599990A (en) * 1967-12-30 1970-07-20
US4347076A (en) * 1980-10-03 1982-08-31 Marko Materials, Inc. Aluminum-transition metal alloys made using rapidly solidified powers and method
EP0100287A1 (en) * 1982-07-06 1984-02-08 CNRS, Centre National de la Recherche Scientifique Amorphous or microcrystalline alloys based on aluminium

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4915748A (en) * 1982-09-03 1990-04-10 Alcan International Aluminum alloys
FR2584095A1 (en) * 1985-06-28 1987-01-02 Cegedur AL ALLOYS WITH HIGH LI AND SI CONTENT AND METHOD OF MANUFACTURE
EP0208631A1 (en) * 1985-06-28 1987-01-14 Cegedur Societe De Transformation De L'aluminium Pechiney Aluminium alloys with a high lithium and silicon content, and process for their manufacture
EP0218035A1 (en) * 1985-10-02 1987-04-15 Allied Corporation Rapidly solidified aluminum based, silicon containing, alloys for elevated temperature applications
US4878967A (en) * 1985-10-02 1989-11-07 Allied-Signal Inc. Rapidly solidified aluminum based, silicon containing alloys for elevated temperature applications
WO1988007592A1 (en) * 1987-03-30 1988-10-06 Allied-Signal Inc. Rapidly solidified aluminum based alloys containing silicon for elevated temperature applications

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NO162426B (en) 1989-09-18
EP0143727A3 (en) 1985-07-10
FR2555610B1 (en) 1987-10-16
FR2555610A1 (en) 1985-05-31
KR850004122A (en) 1985-07-01
ES8602149A1 (en) 1985-11-01
NO162426C (en) 1989-12-27
DE3464387D1 (en) 1987-07-30
IL73645A0 (en) 1985-02-28
NO844743L (en) 1985-05-30
ES538034A0 (en) 1985-11-01
EP0143727B1 (en) 1987-06-24
JPS60215730A (en) 1985-10-29
IL73645A (en) 1987-10-30

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