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EP0100287A1 - Amorphous or microcrystalline alloys based on aluminium - Google Patents

Amorphous or microcrystalline alloys based on aluminium Download PDF

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Publication number
EP0100287A1
EP0100287A1 EP83420113A EP83420113A EP0100287A1 EP 0100287 A1 EP0100287 A1 EP 0100287A1 EP 83420113 A EP83420113 A EP 83420113A EP 83420113 A EP83420113 A EP 83420113A EP 0100287 A1 EP0100287 A1 EP 0100287A1
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Prior art keywords
alloys
amorphous
essentially amorphous
microcrystallized
alloy
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EP0100287B1 (en
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Gérard Le Caer
Jean-Marie Dubois
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Centre National de la Recherche Scientifique CNRS
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    • 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 essentially amorphous or microcrystalline Al-based alloys.
  • alloys in the amorphous state obtained by rapid cooling at a speed generally greater than 10 5 ° C / sec from a disordered state (liquid or vapor).
  • Particularly known are the alloys of type T i X j in which T represents one or more transition metals (in particular iron) and X one or more metalloides (or not) such as B, P, Si, C, Al with i ⁇ 50 at%.
  • T represents one or more transition metals (in particular iron)
  • X one or more metalloides (or not)
  • B, P, Si, C, Al with i ⁇ 50 at% In these alloys, Al intervenes as a minor element whose content in general of the order of 10 at%, does not exceed 35 at%.
  • amorphous alloys have been developed by A. INOUE et al (Journal of Mat. Science, 16, 1981, p. 1895) but relate to the systems (Fe, Co, Ni) -Al-B which may contain up to 60 at. Al and in general from 15 to 45-50 at. % B.
  • the invention therefore relates to alloys based on boron-free Al, which can be obtained in an essentially amorphous or microcrystalline state, by cooling at speeds of the order of 10 to 10 6 K / sec, which 'It is possible to obtain industrially, from a liquid or gaseous state.
  • essentially amorphous alloy is meant a state in which the atoms have no order at long distance, characterized by broad X-ray diffraction spectra and diffusa in the absence of lines characteristic of the crystallized state; the corresponding electron microscopy examinations show that more than 80% by volume of the alloy is amorphous.
  • microcrystalline state means an alloy in which 20% of the volume or more is in the crystallized state and the average size of the crystallites of which is less than 1000 nm, preferably less than 100 nm (1000 A). This average dimension is evaluated from the width at mid-height of the line of the dense planes of the alloy, or by electron microscopy (in black field). In this state, the diffraction lines at small angles ( ⁇ ⁇ '22 °) have disappeared.
  • Microcrystalline alloys are generally obtained either directly from the liquid state, or by crystallization heat treatment above the starting crystallization temperature Tc of the amorphous alloy (this was determined below by enthal analysis - differential spike with a heating rate of 10 ° C / min.).
  • the alloys according to the invention have the following chemical composition defined by the formula: in which: M representing one or more metals from the group Mn, Ni, Cu, Zr, Ti, V, Cr, Fe, Co with M 'representing the Mo and / or the W with X representing one or more elements of the group Ca, Li, Mg, Ge, Si, Zn with Y representing the inevitable processing impurities such as 0, N, C, H, He, Ga, etc., the overall content of which does not exceed 3 atom%, in particular for the lightest elements, but which are required to preferably below 1 at. %.
  • the content of additives is limited above due to metallurgical considerations (melting temperature, viscosity, surface tension, oxidability, etc.), but also economic (price, availability). Mo and W are limited to 15% because they significantly increase the density and the melting point of the alloy.
  • Essentially amorphous or microcrystalline alloys have been obtained with alloys containing between 6 and 25% at Cu with a value of 15 ⁇ b ⁇ 40 at%, the impurities being kept below 1 at%.
  • compositions include individually, or in combination, from 0.5 to 5 at% Mo, 0.5 to 9 at% Si, 5 to 25 at% V and 7 to 25 at% Ni.
  • Figure 1a represents the diagram of the amorphous alloy ,
  • Figure 1b being an enlarged part of the diagram of Figure 1a.
  • FIG. 1c represents the diffraction diagram of the corresponding crystallized alloy.
  • Figure 2 shows the evolution of the hardness of this amorphous alloy according to the invention as a function of time, when maintained at 150 ° C.
  • the alloy Al 80 Cu 10 Ni 8 Mo 2 obtained above and which has a crystallization temperature Tc 156 ° C and a density of 3.7 g / cm 3 , a ratio of the electrical resistance to the state amorphous with respect to the resistance in the crystallized state at 300 ° K of 7, was subjected to maintenance at 150 ° C;
  • FIG. 2 gives the evolution of the Vickers micro-hardness under 10 g, during this test: it reaches 500 HV approx. after 10 h.
  • the Al 72 Cu 15 V 10 Mo 1 Si 2 alloy prepared as in Example 1 has a crystallization temperature of 360 ° C. and a density of 3.6 g / cm 3 . Its micro-hardness reaches 750 HV after 1/2 hour at 400 ° C and 840.HV after 1/2 hour at 450 ° C.
  • the very high hardnesses are favorable for obtaining powders of very high chemical homogeneity, by grinding.
  • the alloys according to the invention can be obtained according to known techniques in the form of wires, strips, ribbons, sheets or powders in the amorphous state and / or in the microcrystallized state. They can be used either directly or as reinforcing elements of other materials or they can also be used for obtaining surface coatings improving for example the resistance to corrosion or wear.

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Abstract

A substantially amorphous or microcrystalline Al-based alloy, wherein said Al-based alloy is represented by the formula: AlaMbM'cXdYe in which: a+b+c+d+e=100 50</=a</=95 atom % 0</=b</=40 atom % 0</=c</=15 atom % 0</=d</=20 atom % 0</=e</=3 atom % wherein at least two of the subscripts b, c or d are strictly positive, and wherein M is at least one metal selected from the group consisting of Mn, Ni, Cu, Zr, Cr, Ti, V, Fe and Co; M' is Mo, W, or a mixture thereof, X is at least one element selected from the group consisting of Ca, Li, Mg, Ge, Si, and Zn; and Y is the inevitable production impurities, with the proviso that when element M is Co, Mn and/or Ni, the total amount of these elements is at least 12 wt % of the alloy.

Description

L'invention se rapporte aux alliages à base d'Al essentiellement amorphes ou microcristallins.The invention relates to essentially amorphous or microcrystalline Al-based alloys.

Il existe de nombreux alliages à l'état amorphe, obtenus par refroidissement rapide à une vitesse en général supérieure à 105°C/sec à partir d'un état désordonné (liquide ou vapeur). On connaît, en particulier, les alliages de type TiXj dans lesquels T représente un ou plusieurs métaux de transition (en particulier le fer) et X un ou plusieurs mé- talloides (ou non) tels que B, P, Si, C, Al avec i ≥ 50 at %. Dans ces alliages, l'Al intervient comme élément mineur dont la teneur en général de l'ordre de 10 at %, ne dépasse pas 35 at %.There are many alloys in the amorphous state, obtained by rapid cooling at a speed generally greater than 10 5 ° C / sec from a disordered state (liquid or vapor). Particularly known are the alloys of type T i X j in which T represents one or more transition metals (in particular iron) and X one or more metalloides (or not) such as B, P, Si, C, Al with i ≥ 50 at%. In these alloys, Al intervenes as a minor element whose content in general of the order of 10 at%, does not exceed 35 at%.

Pour les alliages à base d'Al (contenant plus de 50 % at Al), la littérature technique rapporte des tentatives d'obtention d'alliages amorphes qui ont été effectuées sur des alliages binaires contenant du Bi, du Cd, du Cu, du Ge, de l'In, du Mg, du Ni, du Pd, du Si, du Cr, de l'Ag ou du Zn, mais seuls quatre d'entre eux Al-Ge, Al-Pd, Al-Ni, Al-Cr se sont révélés très localement amorphes (régions visibles en microscopie électronique) et ce, pour de très grandes vitesses de refroidissement de l'ordre de 109 à 1010K/sec, très difficiles à atteindre industriellement - voir T.R. ANANTHARAMAN et al. -"Rapidiy Quenched Metals III" - volume 1-Editor B. Cantor, The Metals Society, Londres (1978) p. 126 et P.FURRER et WARLIMONT, Mat. Science and Eng., 28 (1977) p. 127.For alloys based on Al (containing more than 50% at Al), the technical literature reports attempts to obtain amorphous alloys which have been carried out on binary alloys containing Bi, Cd, Cu, Ge, In, Mg, Ni, Pd, Si, Cr, Ag or Zn, but only four of them Al-Ge, Al-Pd, Al-Ni, Al -Cr have proven to be very locally amorphous (regions visible in electron microscopy) and this, for very high cooling rates of the order of 10 9 to 10 10 K / sec, very difficult to achieve industrially - see TR ANANTHARAMAN et al . - "Rapidiy Quenched Metals III" - volume 1-Editor B. Cantor, The Metals Society, London (1978) p. 126 and P.FURRER and WARLIMONT, Mat. Science and Eng., 28 (1977) p. 127.

Pour les alliages ternaires, des alliages amorphes ont été élaborés par A. INOUE et al (Journal of Mat. Science, 16, 1981, p. 1895) mais sont relatifs aux systèmes (Fe, Co, Ni) -Al-B pouvant contenir jusqu'à 60 at. Al et en général de 15 à 45-50 at. % B.For ternary alloys, amorphous alloys have been developed by A. INOUE et al (Journal of Mat. Science, 16, 1981, p. 1895) but relate to the systems (Fe, Co, Ni) -Al-B which may contain up to 60 at. Al and in general from 15 to 45-50 at. % B.

L'invention concerne donc des alliages à base d'Al exempt de bore,que l'on peut obtenir à l'état essentiellement amorphe ou microcristallin, par refroidissement à des vitesses de l'ordre de 10 à 106 K/sec, qu'il est possible d'obtenir industriellement, à partir d'un état liquide ou gazeux.The invention therefore relates to alloys based on boron-free Al, which can be obtained in an essentially amorphous or microcrystalline state, by cooling at speeds of the order of 10 to 10 6 K / sec, which 'It is possible to obtain industrially, from a liquid or gaseous state.

Par alliage essentiellement amorphe, on entend un état dans lequel les atomes ne présentent aucun ordre à grande distance, caractérisé par des spectres de diffraction des rayons X larges et diffusa en l'absence de raies caractéristiques de l'état cristallisé; les examens en microscopie électronique correspondants montrent que plus de 80 % en volume de l'alliage est amorphe.By essentially amorphous alloy is meant a state in which the atoms have no order at long distance, characterized by broad X-ray diffraction spectra and diffusa in the absence of lines characteristic of the crystallized state; the corresponding electron microscopy examinations show that more than 80% by volume of the alloy is amorphous.

Par état microcristallin, on entend un alliage dans lequel 20 % du volume ou plus est à l'état cristallisa et dont la dimension moyenne des cristallites est inférieure à 1 000 nm, de préférence inférieure à 100 nm (1 000 A). Cette dimension moyenne est évaluée à partir de la largeur à mi-hauteur de la raie des plans denses de l'alliage, ou par microscopie électronique (en champ noir). Dans cet état, les raies de diffraction aux petits angles (θ <'22°) ont disparu.The term “microcrystalline state” means an alloy in which 20% of the volume or more is in the crystallized state and the average size of the crystallites of which is less than 1000 nm, preferably less than 100 nm (1000 A). This average dimension is evaluated from the width at mid-height of the line of the dense planes of the alloy, or by electron microscopy (in black field). In this state, the diffraction lines at small angles (θ <'22 °) have disappeared.

Les alliages microcristallins sont obtenus généralement soit directement à partir de l'état liquide, soit par traitement thermique de cristallisation au-dessus de la température de cristallisation commençante Tc de l'alliage amorphe (celle-ci a été déterminée ci-après par analyse enthal- pique différentielle avec une vitesse de chauffage de 10°C/min.).Microcrystalline alloys are generally obtained either directly from the liquid state, or by crystallization heat treatment above the starting crystallization temperature Tc of the amorphous alloy (this was determined below by enthal analysis - differential spike with a heating rate of 10 ° C / min.).

Les alliages selon l'invention possèdent la composition chimique suivante définie par la formule :

Figure imgb0001
ians laquelle :
Figure imgb0002
M représentant un ou plusieurs métaux du groupe Mn, Ni, Cu, Zr, Ti, V, Cr, Fe, Co avec
Figure imgb0003
M' représentant le Mo et/ou le W avec
Figure imgb0004
X représentant un ou plusieurs éléments du groupe Ca, Li, Mg, Ge, Si, Zn avec
Figure imgb0005
Y représentant les impuretés d'élaboration inévitables telles que 0, N, C, H, He, Ga, etc.. dont la teneur globale ne dépasse pas 3 atomes %, en particulier pour les éléments les plus légers, mais qui sont tenues de préférence en-dessous de 1 at. %.The alloys according to the invention have the following chemical composition defined by the formula:
Figure imgb0001
 in which:
Figure imgb0002
 M representing one or more metals from the group Mn, Ni, Cu, Zr, Ti, V, Cr, Fe, Co with
Figure imgb0003
 M 'representing the Mo and / or the W with
Figure imgb0004
 X representing one or more elements of the group Ca, Li, Mg, Ge, Si, Zn with
Figure imgb0005
 Y representing the inevitable processing impurities such as 0, N, C, H, He, Ga, etc., the overall content of which does not exceed 3 atom%, in particular for the lightest elements, but which are required to preferably below 1 at. %.

La teneur en éléments d'addition est limitée supérieurement en raison de considérations métallurgiques (température de fusion, viscosité, tension superficielle, oxydabilité, etc...), mais aussi économiques (prix, disponibilité). Le Mo et le W sont limités à 15 % car ils augmentent notablement la densité et le point de fusion de l'alliage.The content of additives is limited above due to metallurgical considerations (melting temperature, viscosity, surface tension, oxidability, etc.), but also economic (price, availability). Mo and W are limited to 15% because they significantly increase the density and the melting point of the alloy.

I1 a été constaté qu'il est plus facile d'obtenir un alliage essentiellement amorphe ou microcristallin si la teneur en Al est limitée supérieurement à 85 at %.It has been found that it is easier to obtain an essentially amorphous or microcrystalline alloy if the Al content is limited above 85 at%.

Des alliages essentiellement amorphes ou microcristallins ont été obtenus avec des alliages contenaht entre 6 et 25 % at de Cu avec une valeur de 15 ≤ b ≤ 40 at %, les impuretés étant maintenues inférieures à 1 at %.Essentially amorphous or microcrystalline alloys have been obtained with alloys containing between 6 and 25% at Cu with a value of 15 ≤ b ≤ 40 at%, the impurities being kept below 1 at%.

Des compositions préférentielles comprennent individuellement, ou en combinaison, de 0,5 à 5 at % Mo, 0,5 à 9 at % Si, 5 à 25 at % V et 7 à 25 at % Ni.Preferred compositions include individually, or in combination, from 0.5 to 5 at% Mo, 0.5 to 9 at% Si, 5 to 25 at% V and 7 to 25 at% Ni.

Les figures et exemples illustrent l'invention.The figures and examples illustrate the invention.

La figure 1 montre le diagramme des rayons X d'un alliage Al80Cu10Ni8 MO2, obtenu à l'aide de radiation monomochromatique du Co (λ = 0,17889nm) La figure 1a représente le diagramme de l'alliage amorphe, la figure 1b étant une partie agrandie du diagramme de la figure 1a.Figure 1 shows the X-ray diagram of an Al 80 Cu 10 Ni 8 MO 2 alloy, obtained using monomochromatic radiation of Co (λ = 0.17889nm) Figure 1a represents the diagram of the amorphous alloy , Figure 1b being an enlarged part of the diagram of Figure 1a.

La figure 1c représente le diagramme de diffraction de l'alliage cristallisé correspondant.FIG. 1c represents the diffraction diagram of the corresponding crystallized alloy.

La figure 2 représente l'évolution de la dureté de cet alliage amorphe conforme à l'invention en fonction du temps, lors d'un maintien à 150°C.Figure 2 shows the evolution of the hardness of this amorphous alloy according to the invention as a function of time, when maintained at 150 ° C.

EXEMPLE 1 :EXAMPLE 1:

Divers alliages ont été coulés sous hélium à 30 kPa (0,3 bar) à partir d'un bain liquide, maintenu dans un creuset en quartz, sur l'extérieur d'un tambour en acier doux de 25 cm de diamètre, tournant à 3 000 t/mn (V ≃ 40 m/sec) de manière à obtenir un ruban de 2 mm x 20 µm environ de section transversale.Various alloys were cast under helium at 30 kPa (0.3 bar) from of a liquid bath, held in a quartz crucible, on the outside of a 25 cm diameter mild steel drum, rotating at 3000 rpm (V ≃ 40 m / sec) so as to obtain a tape of approximately 2 mm x 20 µm cross section.

Les résultats de micro-dureté et/ou d'examen aux rayons X obtenus sur ceux-ci sont reportés au tableau I ci-après.The results of micro-hardness and / or X-ray examination obtained thereon are given in Table I below.

EXEMPLE 2 :EXAMPLE 2:

L'alliage Al80Cu10Ni8Mo2 obtenu ci-dessus et qui présente une température de cristallisation Tc = 156° C et une masse volumique de 3,7 g/cm3, un rapport de la résistance électrique à l'état amorphe par rapport à la résistance à l'état cristallisé à 300°K de 7, a été soumis à un maintien à 150° C; la figure 2 donne l'évolution de la micro-dureté Vickers sous 10 g, lors de cet essai : celle-ci atteint 500 HV env. au bout de 10 h.The alloy Al 80 Cu 10 Ni 8 Mo 2 obtained above and which has a crystallization temperature Tc = 156 ° C and a density of 3.7 g / cm 3 , a ratio of the electrical resistance to the state amorphous with respect to the resistance in the crystallized state at 300 ° K of 7, was subjected to maintenance at 150 ° C; FIG. 2 gives the evolution of the Vickers micro-hardness under 10 g, during this test: it reaches 500 HV approx. after 10 h.

EXEMPLE 3 :EXAMPLE 3:

L'alliage Al72Cu15V10Mo1Si2 préparé comme dans l'exemple 1 présente une température de cristallisation de 360° C et une masse volumique de 3,6 g/cm3. Sa micro-dureté atteint 750 HV après maintien de 1/2 h à 400°C et 840.HV après maintien de 1/2 h à 450° C.The Al 72 Cu 15 V 10 Mo 1 Si 2 alloy prepared as in Example 1 has a crystallization temperature of 360 ° C. and a density of 3.6 g / cm 3 . Its micro-hardness reaches 750 HV after 1/2 hour at 400 ° C and 840.HV after 1/2 hour at 450 ° C.

Les duretés très élevées sont favorables à l'obtention de poudres d'une très grande homogénéité chimique, par broyage.The very high hardnesses are favorable for obtaining powders of very high chemical homogeneity, by grinding.

Les alliages suivant l'invention peuvent être obtenus suivant des techniques connues sous forme de fils, bandes, rubans, feuilles ou poudres à l'état amorphe et/ou à l'état micro-cristallisé. Ils peuvent être utilisés soit directement, soit comme éléments de renforcement d'autres matériaux ou encore ils peuvent également être utilisés pour l'obtention de revêtements superficiels améliorant par exemple la résistance à la corrosion ou à l'usure.The alloys according to the invention can be obtained according to known techniques in the form of wires, strips, ribbons, sheets or powders in the amorphous state and / or in the microcrystallized state. They can be used either directly or as reinforcing elements of other materials or they can also be used for obtaining surface coatings improving for example the resistance to corrosion or wear.

Figure imgb0006
Figure imgb0006
Figure imgb0007
Figure imgb0007

Claims (8)

1. - Alliages essentiellement amorphes ou microcristallisés à base d'Al, caractérisés en ce qu'ils sont représentés par la formule :
Figure imgb0008
dans laquelle :
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
avec M représentant un ou plusieurs métaux du groupe Mn, Ni, Cu, Zr, Cr, Ti, V, Fe, Co, M' représentant le Mo et/ou le W, X représentant un ou plusieurs éléments du groupe Ca, Li, Mg, Ge, Si, Zn, Y représentant les impuretés d'élaboration inévitables.1. - Essentially amorphous or microcrystallized alloys based on Al, characterized in that they are represented by the formula:
Figure imgb0008
 in which :
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
 with M representing one or more metals from the group Mn, Ni, Cu, Zr, Cr, Ti, V, Fe, Co, M 'representing the Mo and / or W, X representing one or more elements from the group Ca, Li, Mg, Ge, Si, Zn, Y representing the inevitable processing impurities. 2. - Alliages essentiellement amorphes ou microcristallisés selon la revendication 1, caractérisés en ce que
Figure imgb0015
 2. - Essentially amorphous or microcrystallized alloys according to claim 1, characterized in that
Figure imgb0015
 3. - Alliages essentiellement amorphes ou microcristallisés selon la revendication 1 ou 2, caractérisés en ce que :
Figure imgb0016
Figure imgb0017
et
Figure imgb0018
 3. - Essentially amorphous or microcrystallized alloys according to claim 1 or 2, characterized in that:
Figure imgb0016
Figure imgb0017
 and
Figure imgb0018
 4. - Alliages essentiellement amorphes ou microcristallisés selon la revendication 3, caractérisés en ce que la teneur en Mo est comprise entre 0,5 et 5 at %;4. - Essentially amorphous or microcrystallized alloys according to claim 3, characterized in that the Mo content is between 0.5 and 5 at%; 5. - Alliages essentiellement amorphes ou microcristallisés selon la revendication 3 ou 4, caractérisés en ce que la teneur en Si est comprise entre 0,5 et 9 at %.5. - Essentially amorphous or microcrystallized alloys according to claim 3 or 4, characterized in that the Si content is between 0.5 and 9 at%. 6. - Alliages essentiellement aimrphes à l'état brut de coulée selon l'une des revendications 3 à 5, caractérisés en ce que la teneur en V est comprise entre 5 et 25 at %.6. - Alloys essentially amorphous in the raw casting state according to one of claims 3 to 5, characterized in that the V content is between 5 and 25 at%. 7. - Alliages essentiellement amorphes à l'état brut de coulée selon l'une des revendications 3 à 5, caractérisés en ce que la teneur en Ni est comprise entre 7 et 25 at %.7. - Essentially amorphous alloys in the raw casting state according to one of claims 3 to 5, characterized in that the Ni content is between 7 and 25 at%. 8. - Alliages microcristallisés selon l'une des revendications 1 à 5, caractérisés en ce que la grosseur de grain est inférieure à 1 OOO nm et, de préférence, 100 nm.8. - Microcrystallized alloys according to one of claims 1 to 5, characterized in that the grain size is less than 1 OOO nm and, preferably, 100 nm.
EP83420113A 1982-07-06 1983-07-04 Amorphous or microcrystalline alloys based on aluminium Expired EP0100287B1 (en)

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FR2555610A1 (en) * 1983-11-29 1985-05-31 Cegedur ALUMINUM ALLOYS HAVING HIGH HOT STABILITY
EP0159511A1 (en) * 1984-04-04 1985-10-30 Allied Corporation Aluminum-iron-vanadium alloys having high strength at elevated temperatures
EP0170963A2 (en) * 1984-08-10 1986-02-12 AlliedSignal Inc. Rapidly solifified aluminum-transition metal-silicon alloys
FR2577941A1 (en) * 1985-02-27 1986-08-29 Pechiney AMORPHO ALLOY ALLOYS CONTAINING ESSENTIALLY NI AND / OR FE AND IS AND PROCESS FOR OBTAINING THE SAME
EP0195341A1 (en) * 1985-03-11 1986-09-24 Yoshida Kogyo K.K. Highly corrosion-resistant and high strength aluminum alloys
EP0218035A1 (en) * 1985-10-02 1987-04-15 Allied Corporation Rapidly solidified aluminum based, silicon containing, alloys for elevated temperature applications
WO1988003179A1 (en) * 1986-10-21 1988-05-05 The Secretary Of State For Defence In Her Britanni Rapid solidification route aluminium alloys containing chromium
WO1988007592A1 (en) * 1987-03-30 1988-10-06 Allied-Signal Inc. Rapidly solidified aluminum based alloys containing silicon for elevated temperature applications
EP0289835A1 (en) * 1987-04-28 1988-11-09 Yoshida Kogyo K.K. Amorphous aluminum alloys
WO1988009825A1 (en) * 1987-06-05 1988-12-15 Allied-Signal Inc. Rapidly solidified aluminum iron silicon vanadium alloys
EP0303100A1 (en) * 1987-08-12 1989-02-15 Ykk Corporation High strength, heat resistant aluminum alloys and method of preparing wrought article therefrom
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US5198042A (en) * 1990-11-16 1993-03-30 Tsuyoshi Masumoto Aluminum alloy powders for coating materials, and coating materials containing the alloy powders
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CA1214665A (en) 1986-12-02
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EP0100287B1 (en) 1986-11-12
NO832458L (en) 1984-01-09
ATE23565T1 (en) 1986-11-15
US4710246A (en) 1987-12-01
NO160862C (en) 1989-06-07
FR2529909A1 (en) 1984-01-13
DK310083D0 (en) 1983-07-05
DE3367622D1 (en) 1987-01-02
IL69123A0 (en) 1983-10-31
US4595429A (en) 1986-06-17
JPS5920442A (en) 1984-02-02
DK310083A (en) 1984-01-07
IL69123A (en) 1987-03-31
FR2529909B1 (en) 1986-12-12

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