EP0576366B1 - Metallic coatings consisting of amorphous wear- and corrosion resistant alloys, process for obtaining these alloys and use as wear resistant coatings of hydraulic material - Google Patents

Metallic coatings consisting of amorphous wear- and corrosion resistant alloys, process for obtaining these alloys and use as wear resistant coatings of hydraulic material Download PDF

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Publication number
EP0576366B1
EP0576366B1 EP93420202A EP93420202A EP0576366B1 EP 0576366 B1 EP0576366 B1 EP 0576366B1 EP 93420202 A EP93420202 A EP 93420202A EP 93420202 A EP93420202 A EP 93420202A EP 0576366 B1 EP0576366 B1 EP 0576366B1
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resistant
wear
corrosion
alloys
amorphous metal
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French (fr)
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EP0576366A1 (en
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Jean-Marie Dubois
Philippe Plaindoux
Jean-Pierre Houin
Jean-Marie Roman
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GE Hydro France SAS
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GEC Alsthom Neyrpic
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/008—Amorphous alloys with Fe, Co or Ni as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements

Definitions

  • the present invention relates to metallic coatings based on wear-resistant and corrosion-resistant amorphous alloys, the processes for obtaining these coatings and their applications to the production of anti-wear coatings, in particular for hydraulic equipment.
  • One of the solutions for obtaining materials having a satisfactory compromise between these contradictory properties consists in using metal alloys of amorphous structure obtained by rapid cooling.
  • the amorphous alloys used to date are essentially in the form of small ribbons obtained by a casting method or in the form of very thin deposits obtained by electrochemical methods.
  • the thermal projection methods and for example that of the blown arc plasma have not so far made it possible to obtain completely amorphous alloys at the level of X-ray diffraction in the form of very thick powder deposits (> 0.5 mm) on surfaces up to several square meters.
  • the object of the present invention is to provide amorphous metallic coatings combining with high mechanical characteristics a certain ductility, a high crystallization temperature, a good ability to be released from the residual manufacturing constraints by means of a heat treatment of stress relaxation without causing a significant change in structure and brittleness, good corrosion resistance, including in the presence of halogens, made from alloys capable of being amorphizable for cooling rates of the around 105K / sec., these coatings can be obtained in thicknesses from 0.03 to 1.5 mm on large surfaces.
  • the inventors have discovered that the ease of amorphization can be obtained by combining the action of the different states of positive or negative size of certain constituent elements with respect to the basic constituent elements, and in particular by playing on the combined action of B and Zr on a matrix of Fe - Ni and and / or Co.
  • the powders of these alloys are obtained by atomization and, for grain sizes ⁇ 100 ⁇ m, the grains have a completely amorphous structure by X-ray diffraction.
  • the thermal spray deposition method allows reproducibility of deposition and structural conditions.
  • the alloys used for the amorphous metallic coatings resistant to wear and erosion according to the invention have many advantages compared to the alloys of the prior art. First of all, these are easily amorphizable alloys due to the simultaneous presence of boron, an element whose atomic dimension is smaller than that of T atoms, and of Zr, larger than T atoms.
  • the crystallization temperature of these alloys is remarkably high, when compared to that of alloys of the prior art, such as Fe-B alloys and derived alloys (such as Fe - B - C, Fe - B - Si ).
  • This effect which can be attributed to the presence of zirconium, can be further increased by the addition of refractory elements (such as Mo, Ti, V, Nb, Rh ...) or metalloids.
  • refractory elements such as Mo, Ti, V, Nb, Rh .
  • chromium and zirconium make it possible to obtain excellent resistance to corrosion, an effect which can be further reinforced by the addition of various elements, in particular Rh, Nb, Ti, rare earths and phosphorus.
  • these are essentially ductile metallic glasses in a sufficiently low metalloid concentration range, namely: b + g ⁇ 24 at%.
  • the alloys obtained then resist satisfactorily the embrittlement which usually follows in other alloys the heat treatments at the crystallization temperature.
  • Example 1 Elaboration of alloys corresponding to the general formulation of family (II)
  • Alloys corresponding to the formulation of family (II) have been prepared in the liquid state from the constituents, taken separately. For this, fragments of the elements, of commercial purity, were alloyed in the liquid state in a cold hearth furnace placed under helium. The components were heated by high frequency currents. After melting, these alloys are introduced into the inductor of a tape casting machine consisting of a copper wheel 250 mm in diameter having a tangential speed of 35 m / sec. The enclosure containing the wheel is in a helium atmosphere. The crucible is made of quartz with an orifice 0.8 mm in diameter. The injection pressure of the liquid metal is 0.5 bar. The temperature of the liquid metal is measured by optical pyrometry on the upper face of the liquid.
  • the concentration, in atom%, of the chemical elements is as follows: 50 ⁇ Ni ⁇ 75 0 ⁇ Mo ⁇ 5 5 ⁇ Cr ⁇ 25 0 ⁇ Hf ⁇ 5 5 ⁇ Zr ⁇ 15 0 ⁇ If ⁇ 5 5 ⁇ B ⁇ 15 0 ⁇ La ⁇ 4
  • the concentration, in atom%, of the chemical elements is as follows: 10 ⁇ Fe ⁇ 75 5 ⁇ Zr ⁇ 15 0 ⁇ Hf ⁇ 4 10 ⁇ Ni ⁇ 60 5 ⁇ B ⁇ 15 0 ⁇ Nb ⁇ 4 5 ⁇ Cr ⁇ 15 0 ⁇ Mo ⁇ 12 0 ⁇ La ⁇ 4 O ⁇ Ti ⁇ 10
  • Alloys corresponding to the formulation of family (IV) were developed and obtained in the form of ribbons in an identical manner to that which was done for obtaining the alloys of the preceding examples.
  • the concentration, in atom%, of the chemical elements is as follows: 50 ⁇ Co ⁇ 82 5 ⁇ B ⁇ 15 3 ⁇ Ni ⁇ 35 0 ⁇ Mo ⁇ 12 5 ⁇ Zr ⁇ 15 5 ⁇ Cr ⁇ 15 0 ⁇ La ⁇ 4
  • Alloys corresponding to the formulation of family (V) were developed and obtained in the form of ribbons in an identical manner to that which was done for obtaining the alloys of the preceding examples.
  • the concentration, in atom%, of the chemical elements is as follows: 10 ⁇ Fe ⁇ 65 5 ⁇ Cr ⁇ 15 10 ⁇ Co ⁇ 65 5 ⁇ B ⁇ 15 5 ⁇ Zr ⁇ 15 10 ⁇ Ni ⁇ 65 1 ⁇ C ⁇ 5 O ⁇ If ⁇ 5 1 ⁇ P ⁇ 9
  • Example 5 Elaboration of alloys corresponding to the general formulation of the family (V)
  • Alloys corresponding to the formulation of family (V) were developed and obtained in the form of ribbons in an identical manner to that which was done for obtaining the alloys of the preceding examples.
  • the concentration, in atom%, of the chemical elements is as follows: 10 ⁇ Fe ⁇ 50 5 ⁇ Cr ⁇ 15 10 ⁇ Co ⁇ 50 5 ⁇ B ⁇ 15 5 ⁇ Zr ⁇ 15 10 ⁇ Ni ⁇ 50 0 ⁇ C ⁇ 5 O ⁇ If ⁇ 17 0 ⁇ P ⁇ 9
  • the alloys powders of families (II) to (V) were deposited on various metallic substrates such as structural steel, stainless steels, copper-based alloys, by a thermal spraying method, and for example by the method of arc plasma blown under controlled atmosphere and temperature.
  • These projected powders have a particle size between 30 and 100 ⁇ m.
  • the thicknesses, deposited on a sanded substrate, are between 0.03 and 1.5 mm.
  • the coated surfaces are covered over several square meters.
  • the deposits are made under the conditions described in Example 9. However, according to one embodiment of the method according to the invention, instead of working in a controlled atmosphere, in order to prevent any oxidation during the spraying of the molten powders, the only path of the molten particles is protected by an annular jet of nitrogen, concentric with the jet of plasma carrying the particles, and of dimensions slightly greater than this. The deposits can then be carried out in the open air, under partial nitrogen protection.
  • the thermal mass of the part may be sufficient to provide cooling allowing the deposit to have an amorphous structure. This avoids the cryogenic cooling step.
  • the curves represented in FIG. 8 correspond to a composition in at%: Fe20; Ni28; Co20; Cr12; Zr10; B10.
  • Isothermal anneals define the stability domains of amorphous (A) and crystallized (C) structures for a given time and temperature.
  • the curve represented in FIG. 9 illustrates the results for the anisothermal anneals which define the start of the crystallization temperature as a function of the heating rate.
  • the deposits of thickness of the order of 0.5 mm obtained by the thermal spraying method according to the invention have, in the raw state of deposition, a percentage of porosity of the order of 8% measured by treatment d 'picture.
  • This porosity rate can be reduced to close to 0 by a shot peening of the deposit from carbon steel or stainless steel balls with a diameter between 1 and 1.6 mm for a defined peening intensity (Halmen de la Sté Metal Improvment) from 16 to 18 and a recovery rate (Metal Improvment method) of 600%.
  • the deposits were tested under conditions of wear by abrasive erosion identical to that occurring on the materials of hydraulic machines operating in an aqueous medium loaded with fine particles of solid material such as quartz.
  • the wear measured at room temperature for deposition is equivalent to ceramic wear such as, for example, Cr2O3 and is significantly lower than metal alloys such as stellite, stainless steels such as dupleix or martensito-ferritic, as well as commercial steels known as resistant to abrasion.
  • Dry abrasive erosion tests at angles of incidence ranging from 0 to 90 ° give better behavior of the amorphous alloys according to the invention compared to ceramics and other metal alloys.

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Abstract

The finishes of the present invention consist essentially of metal alloys having the general formula: TaCrbZrcBdMeM'fXgIh(I) in which a+b+c+d+e+f+g+h=100 atomic percent; T is Ni, Co, Ni-Co or any combination of at least one of Ni and Co with Fe, wherein 3<Fe<82 at. % and 3<a<85 at. %; M is one or more elements of the group consisting of Mn, Cu, V, Ti, Mo, Ru, Hf, Ta, W, Nb, Rh, wherein 0<e<12 at. %; M' is one or more rare earths, including Y, wherein 0<f<4 at. %; X is one or more metalloids of the group consisting of C, P, Ge and Si, wherein 0<g<17 at. %; I represents inevitable impurities, wherein h<1 at. %, and 5</=b</=25, 5</=c</=15, and 5</=d</=18. Powders obtained from these alloys that are deposited on substrates by thermal projection provide finishes having increased hardness in addition to high ductility and excellent resistance to corrosion. The finishes are suited for applications including hydraulic equipment.

Description

La présente invention concerne des revêtements métalliques à base d'alliages amorphes résistant à l'usure et à la corrosion, les procédés d'obtention de ces revêtements et leurs applications à la réalisation de revêtements antiusure notamment pour matériel hydraulique.The present invention relates to metallic coatings based on wear-resistant and corrosion-resistant amorphous alloys, the processes for obtaining these coatings and their applications to the production of anti-wear coatings, in particular for hydraulic equipment.

Dans la description qui va suivre, ces revêtements seront principalement étudiés dans leurs applications sur des substrats métalliques. Il est bien évident que, sans sortir du cadre de la présente invention, ils présentent également un intérêt tout particulier quand ils sont appliqués à des substrats non métalliques tels que le bois, le papier et les substrats synthétiques.In the description which follows, these coatings will be mainly studied in their applications on metallic substrates. It is obvious that, without departing from the scope of the present invention, they are also of particular interest when they are applied to non-metallic substrates such as wood, paper and synthetic substrates.

On recherche dans de nombreux domaines à résoudre les problèmes posés par les phénomènes d'usure par érosion abrasive, les rayures et les frottements dans des milieux agressifs et les phénomènes de cavitation. Ces problèmes se posent avec une spéciale acuité lorsqu'il s'agit de matériel hydraulique tel que les turbines.There are researches in many fields to solve the problems posed by phenomena of wear by abrasive erosion, scratches and friction in aggressive media and cavitation phenomena. These problems arise with special acuity when it comes to hydraulic equipment such as turbines.

D'une façon générale, les matériaux actuellement utilisés sont durs mais en contre-partie ils sont fragiles et les utilisateurs recherchent des matériaux réunissant les propriétés suivantes :

  • Dureté élevée leur permettant de résister aux phénomènes d'érosion, de frottement et de rayures
  • Bonne ductilité leur permettant de résister aux chocs et aux faibles déformations.
  • Structure homogène leur assurant un bon comportement à la corrosion.
In general, the materials currently used are hard but in return they are fragile and users are looking for materials with the following properties:
  • High hardness allowing them to resist the phenomena of erosion, friction and scratches
  • Good ductility allowing them to resist shocks and small deformations.
  • Homogeneous structure ensuring good corrosion behavior.

A l'heure actuelle, les matériaux dont on dispose, qu'il s'agisse d'aciers à hautes caractéristiques mécaniques, de stellite, de céramiques... ne possédent pas toutes ces propriétés. Notamment, s'ils résistent bien à la corrosion, ils ne possèdent pas de propriétés mécaniques suffisament élevées.Currently, the materials available, whether steels with high mechanical characteristics, stellite, ceramics ... do not have all these properties. In particular, if they resist corrosion well, they do not have sufficiently high mechanical properties.

Une des solutions pour obtenir des matériaux présentant un compromis satisfaisant entre ces propriétés contradictoires consiste à utiliser des alliages métalliques de structure amorphe obtenus par refroidissement rapide.One of the solutions for obtaining materials having a satisfactory compromise between these contradictory properties consists in using metal alloys of amorphous structure obtained by rapid cooling.

Les alliages amorphes utilisés à ce jour se trouvent essentiellement sous forme de rubans de faibles dimensions obtenus par une méthode de coulage ou sous forme de dépôts de très faible épaisseur obtenus par des méthodes électrochimiques.The amorphous alloys used to date are essentially in the form of small ribbons obtained by a casting method or in the form of very thin deposits obtained by electrochemical methods.

Les méthodes de projection thermique et par exemple celle du plasma d'arc soufflé n'ont pas permis jusqu'à présent d'obtenir des alliages totalement amorphes au niveau de la diffraction des rayons X sous forme de dépôts de poudres de forte épaisseur (>0,5 mm) sur des surfaces pouvant atteindre plusieurs mètres carrés.The thermal projection methods and for example that of the blown arc plasma have not so far made it possible to obtain completely amorphous alloys at the level of X-ray diffraction in the form of very thick powder deposits (> 0.5 mm) on surfaces up to several square meters.

Parmi les différents alliages amorphes actuellement connus, ce sont les alliages métaux-métalloïdes à base de fer (alliages Fe-B ou Fe-Cr-P-B) qui donnent les meilleurs résultats au point de vue des caractéristiques mécaniques. Aucun de ces alliages ne permet toutefois de satisfaire aux exigences contradictoires recherchées de résistance mécanique élevée, de résistance à la corrosion et de ductilité.Among the various amorphous alloys currently known, it is the metal-metalloid alloys based on iron (Fe-B or Fe-Cr-P-B alloys) which give the best results from the point of view of mechanical characteristics. None of these alloys, however, makes it possible to satisfy the contradictory requirements sought for high mechanical strength, corrosion resistance and ductility.

Des alliages résistant à l'usure et à la corrosion présentant des teneurs en Fer inférieure à 2 (en poids%) et en Zirconium inférieure à 7 (en poids %) sont décrits dans EP A 0 224 724 et EP A 0 223 135.Wear-resistant and corrosion-resistant alloys with iron contents less than 2 (by weight%) and zirconium contents less than 7 (by weight%) are described in EP A 0 224 724 and EP A 0 223 135.

La présente invention s'est donné pour objet de proposer des revêtements métalliques amorphes associant à des caractéristiques mécaniques élevées une certaine ductilité, une température de cristallisation élevée, une bonne aptitude à être libérés des contraintes résiduelles de fabrication au moyen d'un traitement thermique de relaxation de contraintes sans provoquer pour autant un changement notable de structure et de fragilité, une bonne résistance à la corrosion, y compris en présence d'halogènes, réalisés à partir d'alliages capables d'être amorphisables pour des vitesses de refroidissement de l'ordre de 10⁵K/sec., ces revêtements pouvant être obtenus sur des épaisseurs de 0,03 à 1,5 mm sur de grandes surfaces.The object of the present invention is to provide amorphous metallic coatings combining with high mechanical characteristics a certain ductility, a high crystallization temperature, a good ability to be released from the residual manufacturing constraints by means of a heat treatment of stress relaxation without causing a significant change in structure and brittleness, good corrosion resistance, including in the presence of halogens, made from alloys capable of being amorphizable for cooling rates of the around 10⁵K / sec., these coatings can be obtained in thicknesses from 0.03 to 1.5 mm on large surfaces.

Les inventeurs ont découvert que la facilité d'amorphisation peut être obtenue en conjugant l'action des différents états de taille positive ou négative de certains éléments constitutifs par rapport aux éléments constitutifs de base, et notamment en jouant sur l'action combinée du B et du Zr sur une matrice de Fe - Ni et et/ou Co.The inventors have discovered that the ease of amorphization can be obtained by combining the action of the different states of positive or negative size of certain constituent elements with respect to the basic constituent elements, and in particular by playing on the combined action of B and Zr on a matrix of Fe - Ni and and / or Co.

D'autre part une faible concentration en métalloïdes et l'absence de composés intermétalliques à haut point de fusion permet d'obtenir une ductilité satisfaisante. La présence de Zr permet l'obtention d'une température de cristallisation élevée. Enfin, un dosage convenable de Cr et de Zr permet de lutter contre la corrosion.On the other hand, a low concentration of metalloids and the absence of intermetallic compounds with a high melting point makes it possible to obtain satisfactory ductility. The presence of Zr allows a high crystallization temperature to be obtained. Finally, a suitable dosage of Cr and Zr makes it possible to fight against corrosion.

Les revêtements métalliques amorphes résistant à l'usure et à la corrosion appliqués sur un substrat selon l'invention sont donc caractérisés en ce qu'ils sont essentiellement constitués d'alliages présentant la formule générale suivante :

        T a Crb Zrc Bd M e M' f Xg I h     (I)

  • dans laquelle a + b + c + d + e + f + g + h = 100 % en nombre d'atomes
  • T est Ni, Co, Ni + Co ou tout choix de plus de l'un de ces éléments associé à Fe avec : 3 <Fe<82 % at. et 3 < a < 85 % at.
  • M est un ou plusieurs éléments d'addition pris parmi la liste : Mn, Cu, V, Ti, Mo, Ru, Hf, Ta, W, Nb, Rh avec : 0≤e<12 % at.
  • M' est une ou plusieurs terres rares, Y inclus, avec : 0 ≤ f <4 % at.
  • X est un ou plusieurs métalloïdes choisis parmi C, P, Ge et Si avec : 0 ≤g <17 % at.
    Figure imgb0001
  • et I représente les impuretés d'élaboration inévitables avec : h < 1% at. On a de plus : 5 ≤ b ≤ 25 % at.
    Figure imgb0002
     5 ≤ c ≤15 % at.
    Figure imgb0003
     5 ≤ d < 18 % at.
    Figure imgb0004
The wear-resistant and corrosion-resistant amorphous metallic coatings applied to a substrate according to the invention are therefore characterized in that they essentially consist of alloys having the following general formula:

T a Cr b Zr c B d M e M ' f X g I h (I)

  • in which a + b + c + d + e + f + g + h = 100% in number of atoms
  • T is Ni, Co, Ni + Co or any choice of more than one of these elements associated with Fe with: 3 <Fe <82% at. and 3 <a <85% at.
  • M is one or more addition elements taken from the list: Mn, Cu, V, Ti, Mo, Ru, Hf, Ta, W, Nb, Rh with: 0≤e <12% at.
  • M ' is one or more rare earths, including Y, with: 0 ≤ f <4% at.
  • X is one or more metalloids chosen from C, P, Ge and Si with: 0 ≤g <17% at.
    Figure imgb0001
  • and I represents the unavoidable processing impurities with: h <1% at. We also have: 5 ≤ b ≤ 25% at.
    Figure imgb0002
     5 ≤ c ≤15% at.
    Figure imgb0003
     5 ≤ d <18% at.
    Figure imgb0004

Les poudres de ces alliages sont obtenues par atomisation et, pour des granulométries < 100 µm, les grains ont une structure totalement amorphe par diffraction aux rayons X.The powders of these alloys are obtained by atomization and, for grain sizes <100 μm, the grains have a completely amorphous structure by X-ray diffraction.

La méthode de dépôt par projection thermique permet une reproductibilité des conditions de dépôt et de structure.The thermal spray deposition method allows reproducibility of deposition and structural conditions.

Les alliages utilisés pour les revêtements métalliques amorphes résistant à l'usure et à l'érosion selon l'invention présentent de nombreux avantages par rapport aux alliages de l'art antérieur. Tout d'abord il s'agit d'alliages facilement amorphisables en raison de la présence simultanée de bore, élément dont la dimension atomique est plus faible que celle des atomes T , et de Zr, plus gros que les atomes T.The alloys used for the amorphous metallic coatings resistant to wear and erosion according to the invention have many advantages compared to the alloys of the prior art. First of all, these are easily amorphizable alloys due to the simultaneous presence of boron, an element whose atomic dimension is smaller than that of T atoms, and of Zr, larger than T atoms.

On notera aussi l'introduction d'autres éléments favorisant la tendance à l'amorphisation, tels que les terres rares et / ou les métalloïdes.Note also the introduction of other elements favoring the tendency to amorphization, such as rare earths and / or metalloids.

De plus la température de cristallisation de ces alliages est remarquablement élevée, si on la compare à celle des alliages de la technique antérieure, comme les alliages Fe - B et les alliages dérivés (tels que Fe - B - C, Fe - B - Si).Furthermore, the crystallization temperature of these alloys is remarkably high, when compared to that of alloys of the prior art, such as Fe-B alloys and derived alloys (such as Fe - B - C, Fe - B - Si ).

Cet effet, que l'on peut imputer à la présence de zirconium, peut encore être augmenté par addition d'éléments réfractaires (tels que Mo, Ti, V, Nb, Rh... ) ou de métalloïdes.This effect, which can be attributed to the presence of zirconium, can be further increased by the addition of refractory elements (such as Mo, Ti, V, Nb, Rh ...) or metalloids.

Les effets conjoints du chrome et du zirconium permettent d'obtenir une excellente résistance à la corrosion, effet qui peut encore être renforcé par addition de divers éléments, en particulier Rh, Nb, Ti, les terres rares et le phosphore.The combined effects of chromium and zirconium make it possible to obtain excellent resistance to corrosion, an effect which can be further reinforced by the addition of various elements, in particular Rh, Nb, Ti, rare earths and phosphorus.

Enfin il s'agit de verres métalliques essentiellement ductiles dans un domaine de concentration en métalloïde suffisamment faible, à savoir :
   b + g ≤ 24 at %. Les alliages obtenus résistent alors de façon satisfaisante à la fragilisation qui suit habituellement dans les autres alliages les traitements thermiques à la température de cristallisation.Finally, these are essentially ductile metallic glasses in a sufficiently low metalloid concentration range, namely:
b + g ≤ 24 at%. The alloys obtained then resist satisfactorily the embrittlement which usually follows in other alloys the heat treatments at the crystallization temperature.

Dans la formule générale (I) indiquée ci-avant, le choix de l'élément T permet de distinguer différentes familles d'alliages satisfaisant aux critères de la présente invention.In the general formula (I) indicated above, the choice of the element T makes it possible to distinguish different families of alloys satisfying the criteria of the present invention.

Si T est le nickel, on peut tout d'abord distinguer la famille (Il) qui répond à la formulation :

        Nia Crb Zrc Bd M e M' f X g I h     (II)

  • dans laquelle a + b + c + d + e + f + g + h = 100 % en nombre d'atomes.
  • M, M', X, I représentent les mêmes éléments que ceux mentionnés précédemment pour la formule (I), les compositions étant celles indiquées ci-dessus.
If T is nickel, we can first of all distinguish the family (II) which corresponds to the formulation:

Ni a Cr b Zr c B d M e M ' f X g I h (II)

  • in which a + b + c + d + e + f + g + h = 100% in number of atoms.
  • M, M ', X, I represent the same elements as those mentioned above for formula (I), the compositions being those indicated above.

Une autre famille d'alliages (III) selon l'invention est constituée d'alliages de la famille (Il) ci-dessus dans lesquels une partie des atomes de nickel a été remplacée par du fer, à savoir :

        Nia Fea'Crb Zrc Bd M e M' f X g I h     (III)

  • dans laquelle : 3 < a + a' ≤ 85 at %
  • tous les autres symboles présentant la même signification que précédemment.
Another family of alloys (III) according to the invention consists of alloys of the family (II) above in which part of the nickel atoms has been replaced by iron, namely:

Ni a Fe a ' Cr b Zr c B d M e M' f X g I h (III)

  • where: 3 <a + a '≤ 85 at%
  • all other symbols having the same meaning as above.

La substitution d'une partie du nickel de la famille (Il) ci-dessus par du cobalt permet d'obtenir les alliages de formule générale (IV) :

        Nia Coa" Crb Zrc Bd M e M' f X g I h     (IV)

  • dans laquelle : 3 < a + a" ≤ 85 at %, les autres symboles ayant la même signification que dans la formule (I).
The substitution of part of the nickel of the family (II) above by cobalt makes it possible to obtain the alloys of general formula (IV):

Ni a Co a " Cr b Zr c B d M e M ' f X g I h (IV)

  • in which: 3 <a + a "≤ 85 at%, the other symbols having the same meaning as in formula (I).

On peut enfin distinguer une dernière famille de formule générale (V):

        Nia Fea' Coa" Crb Zrc Bd M e M' f X g I h     (V)

  • dans laquelle : 3 < a +a' + a" ≤ 85 at %.
We can finally distinguish a last family of general formula (V):

Ni a Fe a ' Co a " Cr b Zr c B d M e M' f X g I h (V)

  • in which: 3 <a + a '+ a "≤ 85 at%.

Les exemples suivants permettront de mieux comprendre la présente invention, les caractéristiques qu'elle présente et les avantages qu'elle est susceptible de procurer.The following examples will make it possible to better understand the present invention, the characteristics which it presents and the advantages which it is capable of providing.

Exemple 1: Elaboration d'alliages répondant à la formulation générale de la famille (II)Example 1: Elaboration of alloys corresponding to the general formulation of family (II)

Des alliages répondant à la formulation de la famille (Il) ont été élaborés à l'état liquide à partir des constituants, pris séparément. Pour cela, des fragments des éléments, de pureté commerciale, ont été alliés à l'état liquide dans un four à sole froide placé sous hélium. Le chauffage des constituants a été obtenu par courants haute fréquence. Après fusion, ces alliages sont introduits dans l'inducteur d'une machine de coulage des rubans constituée d'une roue en cuivre de 250 mm de diamètre ayant une vitesse tangentielle de 35 m / sec. L'enceinte contenant la roue est en ambiance d'hélium. Le creuset est en quartz percé d'un orifice de 0,8 mm de diamètre. La pression d'injection du métal liquide est de 0,5 bar. La température du métal liquide est mesurée par pyrométrie optique sur la face supérieure du liquide.Alloys corresponding to the formulation of family (II) have been prepared in the liquid state from the constituents, taken separately. For this, fragments of the elements, of commercial purity, were alloyed in the liquid state in a cold hearth furnace placed under helium. The components were heated by high frequency currents. After melting, these alloys are introduced into the inductor of a tape casting machine consisting of a copper wheel 250 mm in diameter having a tangential speed of 35 m / sec. The enclosure containing the wheel is in a helium atmosphere. The crucible is made of quartz with an orifice 0.8 mm in diameter. The injection pressure of the liquid metal is 0.5 bar. The temperature of the liquid metal is measured by optical pyrometry on the upper face of the liquid.

La concentration , en atomes %, des éléments chimiques est la suivante : 50 ≤ Ni ≤ 75 0 ≤ Mo ≤ 5 5 ≤ Cr ≤ 25 0 ≤ Hf ≤ 5 5 ≤ Zr ≤ 15 0 ≤ Si ≤ 5 5 ≤ B ≤ 15 0 ≤ La ≤ 4 The concentration, in atom%, of the chemical elements is as follows: 50 ≤ Ni ≤ 75 0 ≤ Mo ≤ 5 5 ≤ Cr ≤ 25 0 ≤ Hf ≤ 5 5 ≤ Zr ≤ 15 0 ≤ If ≤ 5 5 ≤ B ≤ 15 0 ≤ La ≤ 4

Une analyse chimique plus précise donne:A more precise chemical analysis gives:

Ni₅₈ ; Cr₂₀ Zr₁₀ ; B₁₀ ; Mo₂, alliage qui a une température de fusion (Tf₀) mesurée par pyrométrie optique de 1127°C et une dureté Hv₃₀ de l'ordre de 480.Ni₅₈; Cr₂₀ Zr₁₀; B₁₀; Mo₂, an alloy which has a melting temperature (Tf₀) measured by optical pyrometry of 1127 ° C and a hardness Hv₃₀ of the order of 480.

Exemple 2 : Elaboration d'alliages répondant à la formulation générale de la famille (III)Example 2: Elaboration of alloys corresponding to the general formulation of the family (III)

Des alliages répondant à la formulation de la famille (III) ont été élaborés et obtenus sous forme de rubans de façon identique à ce qui a été fait pour l'obtention des alliages de l'exemple 1.Alloys corresponding to the formulation of family (III) were developed and obtained in the form of ribbons in an identical manner to that which was done for obtaining the alloys of Example 1.

La concentration, en atomes %, des éléments chimiques est la suivante : 10 ≤ Fe ≤ 75 5 ≤ Zr ≤ 15 0 ≤ Hf ≤ 4 10 ≤ Ni ≤ 60 5 ≤ B ≤ 15 0 ≤ Nb ≤ 4 5 ≤ Cr ≤ 15 0 ≤ Mo ≤ 12 0 ≤ La ≤ 4 O ≤ Ti ≤ 10 The concentration, in atom%, of the chemical elements is as follows: 10 ≤ Fe ≤ 75 5 ≤ Zr ≤ 15 0 ≤ Hf ≤ 4 10 ≤ Ni ≤ 60 5 ≤ B ≤ 15 0 ≤ Nb ≤ 4 5 ≤ Cr ≤ 15 0 ≤ Mo ≤ 12 0 ≤ La ≤ 4 O ≤ Ti ≤ 10

Une analyse chimique plus précise donne

  • Fe₅₁ ; Ni₁₈ ; Cr₈ ; Zr₁₀ ; B₁₂ ; Mo0,3 ; Si0,5 ; Hf0,2, alliage qui a une température de fusion (Tf₀) mesurée par pyrométrie optique de 1100°C et une dureté Hv₃₀ de 585.
  • Ou encore:
  • Fe₆₅ ; Ni₁₀ Cr₅ ; Zr₈ ; B₁₀ ; Ti₂, alliage qui a une température de fusion (Tf₀) mesurée par pyrométrie optique de 1080°C et une dureté Hv₃₀ de 870.
A more precise chemical analysis gives
  • Fe₅₁; Ni₁₈; Cr₈; Zr₁₀; B₁₂; Mo 0.3 ; If 0.5 ; Hf 0.2 , an alloy which has a melting temperature (Tf₀) measured by optical pyrometry of 1100 ° C and an Hv₃₀ hardness of 585.
  • Or:
  • Fe₆₅; Ni₁₀ Cr₅; Zr₈; B₁₀; Ti₂, an alloy which has a melting temperature (Tf₀) measured by optical pyrometry of 1080 ° C and an Hv₃₀ hardness of 870.

Exemple 3 : Elaboration d'alliages répondant à la formulation générale de la famille (IV)Example 3: Elaboration of alloys corresponding to the general formulation of the family (IV)

Des alliages répondant à la formulation de la famille (IV) ont été élaborés et obtenus sous forme de rubans de façon identique à ce qui a été fait pour l'obtention des alliages des exemples précédents.Alloys corresponding to the formulation of family (IV) were developed and obtained in the form of ribbons in an identical manner to that which was done for obtaining the alloys of the preceding examples.

La concentration , en atomes %, des éléments chimiques est la suivante : 50 ≤ Co ≤ 82 5 ≤ B ≤ 15 3 ≤ Ni ≤ 35 0 ≤ Mo ≤ 12 5 ≤ Zr ≤15 5 ≤ Cr ≤ 15 0 ≤ La ≤ 4 The concentration, in atom%, of the chemical elements is as follows: 50 ≤ Co ≤ 82 5 ≤ B ≤ 15 3 ≤ Ni ≤ 35 0 ≤ Mo ≤ 12 5 ≤ Zr ≤15 5 ≤ Cr ≤ 15 0 ≤ La ≤ 4

Une analyse chimique plus précise donne :

  • Co₆₅; Ni₁₀ ; Cr₅ ; Zr₁₂ ; B₈, alliage qui a une température de fusion (Tf₀) mesurée par pyrométrie optique de 1020°C et une dureté Hv₃₀ de 550.
A more precise chemical analysis gives:
  • Co₆₅; Ni₁₀; Cr₅; Zr₁₂; B₈, an alloy which has a melting temperature (Tf₀) measured by optical pyrometry of 1020 ° C and an Hv₃₀ hardness of 550.

Exemple 4 : Elaboration d'alliages répondant à la formulation générale de la famille (V)Example 4: Elaboration of alloys corresponding to the general formulation of the family (V)

Des alliages répondant à la formulation de la famille (V) ont été élaborés et obtenus sous forme de rubans de façon identique à ce qui a été fait pour l'obtention des alliages des exemples précédents.Alloys corresponding to the formulation of family (V) were developed and obtained in the form of ribbons in an identical manner to that which was done for obtaining the alloys of the preceding examples.

La concentration , en atomes %, des éléments chimiques est la suivante : 10 ≤ Fe ≤ 65 5 ≤ Cr ≤ 15 10 ≤ Co ≤ 65 5 ≤ B ≤ 15 5 ≤ Zr ≤ 15 10 ≤ Ni ≤ 65 1 ≤ C ≤ 5 O ≤ Si < 5 1 ≤ P ≤ 9 The concentration, in atom%, of the chemical elements is as follows: 10 ≤ Fe ≤ 65 5 ≤ Cr ≤ 15 10 ≤ Co ≤ 65 5 ≤ B ≤ 15 5 ≤ Zr ≤ 15 10 ≤ Ni ≤ 65 1 ≤ C ≤ 5 O ≤ If <5 1 ≤ P ≤ 9

Une analyse chimique plus précise donne :

  • Fe₃₆ ; Co₁₄ ; Ni₁₇ ; Cr₁₃ ; Zr₇ ; B₇ ; C₃ ; Si0,3 ; P2,7 ,alliage qui a une température de fusion (Tf₀) de 1065°C et une dureté Hv₃₀ de 685.
A more precise chemical analysis gives:
  • Fe₃₆; Co₁₄; Ni₁₇; Cr₁₃; Zr₇; B₇; C₃; If 0.3 ; P 2.7 , an alloy which has a melting temperature (Tf₀) of 1065 ° C and an Hv₃₀ hardness of 685.

Exemple 5 : Elaboration d'alliages répondant à la formulation générale de la famille (V)Example 5: Elaboration of alloys corresponding to the general formulation of the family (V)

Des alliages répondant à la formulation de la famille (V) ont été élaborés et obtenus sous forme de rubans de façon identique à ce qui a été fait pour l'obtention des alliages des exemples précédents.Alloys corresponding to the formulation of family (V) were developed and obtained in the form of ribbons in an identical manner to that which was done for obtaining the alloys of the preceding examples.

La concentration , en atomes %, des éléments chimiques est la suivante : 10 ≤ Fe ≤ 50 5 ≤ Cr ≤ 15 10 ≤ Co ≤ 50 5 ≤ B ≤ 15 5 ≤ Zr ≤ 15 10 ≤ Ni ≤ 50 0 ≤ C ≤ 5 O ≤ Si < 17 0 ≤ P ≤ 9 The concentration, in atom%, of the chemical elements is as follows: 10 ≤ Fe ≤ 50 5 ≤ Cr ≤ 15 10 ≤ Co ≤ 50 5 ≤ B ≤ 15 5 ≤ Zr ≤ 15 10 ≤ Ni ≤ 50 0 ≤ C ≤ 5 O ≤ If <17 0 ≤ P ≤ 9

Une analyse chimique plus précise donne :

  • Fe₁₆ ; Co₁₆ ; Ni₂₀ ; Cr₁₀ ; Zr₁₀; B₁₄ ; Si₁₄ ,alliage qui a une température de fusion (Tf₀) de 1080°C et une dureté Hv₃₀ de 1430.
A more precise chemical analysis gives:
  • Fe₁₆; Co₁₆; Ni₂₀; Cr₁₀; Zr₁₀; B₁₄; Si₁₄, an alloy which has a melting temperature (Tf₀) of 1080 ° C and an Hv₃₀ hardness of 1430.

Les exemples suivants rassemblent les résultats obtenus sur les rubans et les poudres de compositions chimiques décrites dans les exemples précédents, en référence au dessin schématique annexé dans lequel :

  • Fig 1 à 7 sont des courbes de diffraction aux rayons X dans lesquelles les valeurs 2 θ sont portées en abscisse et l'intensité I en ordonnée
  • Fig 8 est une courbe de recuit isotherme dans laquelle le temps (en heures) a été porté en abscisse et la température (en °C) en ordonnée
  • Fig. 9 est une courbe de recuit anisotherme dans laquelle la vitesse de chauffage (en °C.min⁻¹)a été portée en abscisse et la température de début de cristallisation (en °C) en ordonnée.
The following examples bring together the results obtained on the ribbons and powders of chemical compositions described in the previous examples, with reference to the appended schematic drawing in which:
  • Fig 1 to 7 are X-ray diffraction curves in which the values 2 θ are plotted on the abscissa and the intensity I on the ordinate
  • Fig 8 is an isothermal annealing curve in which the time (in hours) has been plotted on the abscissa and the temperature (in ° C) on the ordinate
  • Fig. 9 is an anisothermal annealing curve in which the heating rate (in ° C.min⁻¹) has been plotted on the abscissa and the temperature at the start of crystallization (in ° C) on the ordinate.

Exemple 6Example 6

Les rubans répondant aux compositions indiquées ci-avant possèdent une stabilité thermique très grande que l'on peut vérifier

  • d'une part par la valeur élevée de la température de cristallisation Tx1 qui est par exemple:
  • pour l'ex. 2 Tx1 = 545°C
  • pour l'ex. 3 Tx1 = 570°C
  • pour l'ex. 4 Tx1 = 560°C
    pour une vitesse de chauffage de 20 K/min.
  • d'autre part, par exemple pour la composition : Fe₂₀ ; Co₂₀ ;Ni₂₈ ;Cr ₁₂; Zr₁₀; B₁₀, par le fait qu'un traitement thermique de 3 heures à 400°C ne fait pas apparaître par diffraction aux rayons X de modification de la structure amorphe initiale.
The ribbons corresponding to the compositions indicated above have a very high thermal stability which can be checked.
  • on the one hand by the high value of the crystallization temperature T x1 which is for example:
  • for the ex. 2 T x1 = 545 ° C
  • for the ex. 3 T x1 = 570 ° C
  • for the ex. 4 T x1 = 560 ° C
    for a heating speed of 20 K / min.
  • on the other hand, for example for the composition: Fe₂₀; Co₂₀; Ni₂₈; Cr ₁₂; Zr₁₀; B₁₀, by the fact that a heat treatment of 3 hours at 400 ° C does not reveal by X-ray diffraction a modification of the initial amorphous structure.

Exemple 7 - Résistance à la corrosion d'alliages obtenus sous forme de rubansEXAMPLE 7 Corrosion Resistance of Alloys Obtained in the Form of Ribbons

Pour caractériser cette tenue, on a mesuré les paramètres suivants :

  • Potentiel de dissolution statique et dynamique
  • Résistance de polarisation autour du potentiel de corrosion en mode potentiodynamique et / ou en mode galvanodynamique
  • Intensité du courant de corrosion.
To characterize this outfit, the following parameters were measured:
  • Static and dynamic dissolution potential
  • Polarization resistance around the corrosion potential in potentiodynamic mode and / or in galvanodynamic mode
  • Intensity of the corrosion current.

Ces paramètres ont été déterminés dans les milieux suivants :

  • H₂SO₄ 0,1 N
  • NaOH 0,1 N
  • NaCI à 3 % de concentration dans l'eau.
These parameters have been determined in the following media:
  • H₂SO₄ 0.1 N
  • 0.1 N NaOH
  • NaCI at 3% concentration in water.

On a par exemple pour l'alliage : Fe₆₀ ; Ni₁₀ ; Cr₁₀ ; Zr₈ ; B₁₂ ECorr Mv/ess E Corr dynam. Icorr.Mil.amp/cm Rp K ohm/cm2 N2SO4 0,1 - 556 - 674 0,69 303 NaOH 0,1N - 654 - 660 0 3465 NaCl 3 % - 210 - 90 0 We have for example for the alloy: Fe₆₀; Ni₁₀; Cr₁₀; Zr₈; B₁₂ ECorr Mv / ess E Corr dynam. Icorr.Mil.amp / cm Rp K ohm / cm2 N2SO4 0.1 - 556 - 674 0.69 303 0.1N NaOH - 654 - 660 0 3465 NaCl 3% - 210 - 90 0

Exemple 8Example 8

Les poudres d'alliages des familles (II) à (V) ont été déposées sur différents substrats métalliques tels que acier de construction, aciers inoxydables, alliages à base de cuivre, par une méthode de projection thermique, et par exemple par la méthode du plasma d'arc soufflé sous atmosphère et température contrôlées.The alloys powders of families (II) to (V) were deposited on various metallic substrates such as structural steel, stainless steels, copper-based alloys, by a thermal spraying method, and for example by the method of arc plasma blown under controlled atmosphere and temperature.

Ces poudres projetées ont une granulométrie comprise entre 30 et 100 µm. Les épaisseurs, déposées sur un substrat sablé, sont comprises entre 0,03 et 1,5 mm. Les surfaces revêtues le sont sur plusieurs mètres carrés.These projected powders have a particle size between 30 and 100 μm. The thicknesses, deposited on a sanded substrate, are between 0.03 and 1.5 mm. The coated surfaces are covered over several square meters.

Les clichés de diffraction par rayons X représentés par les courbes des figures 3 (épaisseur 0,1 mm), 4 (épaisseur 0,2 mm), 5 (épaisseur 0,3 mm), 6 (épa!isseur 0,4 mm) et 7 (épaisseur 0,5 mm) , effectués dans les mêmes conditions que celles décrites dans l'exemple 8 mettent en évidence la structure totalement amorphe, en surface et dans l'épaisseur, de ces dépôts.The X-ray diffraction patterns represented by the curves of FIGS. 3 (thickness 0.1 mm), 4 (thickness 0.2 mm), 5 (thickness 0.3 mm), 6 (thickness! Issuer 0.4 mm) and 7 (thickness 0.5 mm), carried out under the same conditions as those described in Example 8, demonstrate the totally amorphous structure, on the surface and in the thickness, of these deposits.

On peut également faire suivre ces dépôts de poudre d'un refroidissement cryogénique dans les conditions décrites par exemple dans le document FR - A 83 07 135.These powder deposits can also be followed by cryogenic cooling under the conditions described for example in the document FR - A 83 07 135.

Exemple 9Example 9

Les dépôts sont effectués dans les conditions décrites dans l'exemple 9. Toutefois, selon un mode de réalisation du procédé selon l'invention, au lieu de travailler en atmosphère contrôlée, afin de prévenir toute oxydation lors de la projection des poudres en fusion, on protège le seul trajet des particules en fusion par un jet annulaire d'azote, concentrique au jet de plasma véhiculant les particules, et de dimensions très légérement supérieures à celui-ci. Les dépôts peuvent alors être effectués à l'air libre, sous protection partielle d'azote.The deposits are made under the conditions described in Example 9. However, according to one embodiment of the method according to the invention, instead of working in a controlled atmosphere, in order to prevent any oxidation during the spraying of the molten powders, the only path of the molten particles is protected by an annular jet of nitrogen, concentric with the jet of plasma carrying the particles, and of dimensions slightly greater than this. The deposits can then be carried out in the open air, under partial nitrogen protection.

Dans le cas des pièces de fortes épaisseurs, la masse thermique de la pièce peut suffire à assurer le refroidissement permettant au dépôt d'avoir une structure amorphe. On évite ainsi l'étape de refroidissement cryogénique.In the case of very thick parts, the thermal mass of the part may be sufficient to provide cooling allowing the deposit to have an amorphous structure. This avoids the cryogenic cooling step.

Exemple 10 - Etude de la stabilité thermique des poudres et des dépôtsExample 10 - Study of the thermal stability of powders and deposits

Sur les dépôts correspondant aux analyses chimiques relatives aux familles (I) à (V) les recuits isothermes et anisothermes montrent l'excellente stabilité thermique des alliages amorphes. Les courbes représentées à la figure 8 correspondent à une composition en at % :

        Fe₂₀ ; Ni₂₈ ; Co₂₀ ; Cr₁₂ ; Zr₁₀ ; B₁₀.

On the deposits corresponding to the chemical analyzes relating to families (I) to (V) the isothermal and anisothermal anneals show the excellent thermal stability of the amorphous alloys. The curves represented in FIG. 8 correspond to a composition in at%:

Fe₂₀; Ni₂₈; Co₂₀; Cr₁₂; Zr₁₀; B₁₀.

Le tableau suivant donne la correspondance avec les concentrations en poids. at % Masse at. Masse d'éléments dans l'alliage Poids % Fe 20 56 1120 20 Ni 28 58,7 1643 29 Co 20 59 1180 21 Cr 12 52 624 11 Zr 10 91,2 912 16 B 10 10,8 108 2 Total 5587 The following table gives the correspondence with the concentrations by weight. at% Mass at. Mass of elements in the alloy Weight% Fe 20 56 1120 20 Or 28 58.7 1643 29 Co 20 59 1180 21 Cr 12 52 624 11 Zr 10 91.2 912 16 B 10 10.8 108 2 Total 5587

Les recuits isothermes définissent les domaines de stabilité des structures amorphes (A) et cristallisées (C) pour un temps et une température donnés.Isothermal anneals define the stability domains of amorphous (A) and crystallized (C) structures for a given time and temperature.

La courbe représentée à la figure 9 illustre les résultats pour les recuits anisothermes qui définissent le début de température de cristallisation en fonction de la vitesse de chauffage.The curve represented in FIG. 9 illustrates the results for the anisothermal anneals which define the start of the crystallization temperature as a function of the heating rate.

Ces résultats montrent l'excellente stabilité des revêtements amorphes jusqu'à des températures très élevées, ce qui est une caractéristique très importante de l'invention.These results show the excellent stability of amorphous coatings up to very high temperatures, which is a very important characteristic of the invention.

Exemple 11Example 11

On a pu déterminer les caractéristiques mécaniques exceptionnelles dont font preuve les dépôts obtenus selon la présente invention, qu'il s'agisse de dureté- ductilité ou de comportement tribologique. Par exemple pour la composition en at % :

        Fe₂₀ ; Ni₂₈ ; Co₂₀ ; Cr₁₂ ; Zn₁₀ ; B₁₀,

  • on a effectué des essais "pion-disc" mesurant le coefficient de frottement moyen entre le matériau et un indenteur en diamant ou en alumine ; on obtient une valeur du coefficient de frottement à sec de l'ordre de 0,11 lorsque le dépôt a subi un revenu de 3 heures à 400°C. L'examen de la trace de l'indenteur dans le dépôt montre que, s'il y a fissures, celles-ci sont du type ductile.
It has been possible to determine the exceptional mechanical characteristics shown by the deposits obtained according to the present invention, whether it be hardness-ductility or tribological behavior. For example for the composition in at%:

Fe₂₀; Ni₂₈; Co₂₀; Cr₁₂; Zn₁₀; B₁₀,

  • "pion-disc" tests were carried out measuring the average coefficient of friction between the material and a diamond or alumina indenter; a value of the dry friction coefficient is obtained of the order of 0.11 when the deposit has undergone a 3 hour tempering at 400 ° C. Examination of the indentor trace in the deposit shows that, if there are cracks, they are of the ductile type.

Sur un dépôt de même analyse chimique mais cristallisé, le coefficient moyen de frottement est plus élevé d'environ 5 % et on met en évidence, lors de l'examen de la trace de l'indenteur, des fissures de type fragile.On a deposit of the same chemical analysis but crystallized, the average coefficient of friction is higher by about 5% and one highlights, during the examination of the trace of the indentor, cracks of fragile type.

Ces observations sont confirmées par l'essai de rayures standard dans lequel, jusqu'à des pressions appliquées de l'ordre de la limite de rupture, on ne met pas en évidence de fissuration.These observations are confirmed by the standard scratch test in which, up to applied pressures of the order of the breaking limit, no cracking is revealed.

Exemple 12Example 12

Les dépôts d'épaisseur de l'ordre de 0,5 mm obtenus par la méthode de projection thermique selon l'invention possèdent, à l'état brut de dépôt, un pourcentage de porosité de l'ordre de 8 % mesuré par traitement d'image.The deposits of thickness of the order of 0.5 mm obtained by the thermal spraying method according to the invention have, in the raw state of deposition, a percentage of porosity of the order of 8% measured by treatment d 'picture.

Ce taux de porosité peut être ramené au voisinage de 0 par un grenaillage du dépôt à partir de billes d'acier carbone ou d'acier inoxydable de diamètre compris entre 1 et 1,6 mm pour une intensité de grenaillage définie (Halmen de la Sté Metal Improvment) de 16 à 18 et un taux de recouvrement (méthode de Metal Improvment) de 600 %.This porosity rate can be reduced to close to 0 by a shot peening of the deposit from carbon steel or stainless steel balls with a diameter between 1 and 1.6 mm for a defined peening intensity (Halmen de la Sté Metal Improvment) from 16 to 18 and a recovery rate (Metal Improvment method) of 600%.

Ce résultat est confirmé par l'étude de perméabilité du dépôt par méthode électrochimique mettant en évidence, pour des conditions de corrosion sévères telles qu'indiquées précédemment, la non corrosion de l'acier au carbone servant de substrat au dépôt. Le dépôt est imperméable à l'électrolyte.This result is confirmed by the study of permeability of the deposit by electrochemical method highlighting, for severe corrosion conditions as indicated above, the non-corrosion of the carbon steel serving as a substrate for the deposit. The deposit is impermeable to the electrolyte.

Exemple 13Example 13

Les dépôts ont été testés dans des conditions d'usure par érosion abrasive identique à celle se produisant sur les matériaux de machines hydrauliques fonctionnant en milieu aqueux chargé en particules fines de matériau solide telles que le quartz.The deposits were tested under conditions of wear by abrasive erosion identical to that occurring on the materials of hydraulic machines operating in an aqueous medium loaded with fine particles of solid material such as quartz.

Des essais comparatifs ont été faits avec d'autres matériaux dans les conditions suivantes :

  • Ecoulement tangentiel et aussi avec un angle d'incidence liquide-pièce < 45
  • Vitesse d'écoulement ≥ 48 m/s.
  • Concentration en quartz de granulométrie = 200 µ de 20 g/l.
Comparative tests were made with other materials under the following conditions:
  • Tangential flow and also with a liquid-part angle of incidence <45
  • Flow velocity ≥ 48 m / s.
  • Concentration in quartz with grain size = 200 µ of 20 g / l.

Les usures mesurées à température ambiante pour le dépôt sont équivalentes aux usures de céramiquetelles que, par exemple, Cr₂O₃ et sont nettement inférieures aux alliages métallique type stellite, aciers inoxydables types dupleix ou martensito-ferritique, ainsi qu'aux aciers du commerce dits résistants à l'abrasion.The wear measured at room temperature for deposition is equivalent to ceramic wear such as, for example, Cr₂O₃ and is significantly lower than metal alloys such as stellite, stainless steels such as dupleix or martensito-ferritic, as well as commercial steels known as resistant to abrasion.

Les essais en érosion abrasive à sec sous des angles d'incidence allant de 0 à 90° donnent un meilleur comportement des alliages amorphes selon l'invention par rapport aux céramiques et autres alliages métalliques.Dry abrasive erosion tests at angles of incidence ranging from 0 to 90 ° give better behavior of the amorphous alloys according to the invention compared to ceramics and other metal alloys.

L'examen de la structure par diffraction aux rayons X montre que le dépôt a conservé une stucture amorphe similaire à celle du départ.Examination of the structure by X-ray diffraction shows that the deposit has retained an amorphous structure similar to that at the start.

Enfin on obtient également d'excellents résultats quand les dépôts sont appliqués sur des substrats non métalliques : bois, papier, substrats synthétiques.Finally, excellent results are also obtained when the deposits are applied to non-metallic substrates: wood, paper, synthetic substrates.

Claims (13)

  1. Wear-resistant and corrosion-resistant amorphous metal coatings applied to a substrate, characterised in that they essentially comprise metal alloys of the general formula:

            Ta Crb Zrc Bd Me M'f Xg Ih     (I)

    in which a + b + c + d + e + f + g + h = 100% in numbers of atoms,
    T is Ni, Co, Ni + Co, or any selection of more than one of these elements associated with Fe, where: 3 < Fe < 82% at. and 3 < a < 85% at.,
    M is one or more added elements selected from the list: Mn, Cu, V, Ti, Mo, Ru, Hf, Ta, W, Nb, Rh, where 0 ≤ e ≤ 12% at., M' is one or more rare earths, including Y, where: 0 ≤ f < 4% at.,
    X is one or more metalloids selected from C, P, Ge and Si, where: 0 ≤ g < 17% at.,
    I represents unavoidable processing impurities, where: h < 1% at. and 5 ≤ b ≤ 25% at
    Figure imgb0010
     5 ≤ c 15% at
    Figure imgb0011
     5 ≤ d < 18% at
    Figure imgb0012
  2. Wear-resistant and corrosion-resistant amorphous metal coatings according to claim 1, characterised in that the metal alloys have the general formula:

            Nia Crb Zrc Bd M e M' f X g I h     (II)

    in which a + b + c + d + e + f + g + h = 100% by number of atoms. M, M', X, I represent the same elements as those mentioned in formula (I), the compositions being those indicated above.
  3. Wear-resistant and corrosion-resistant amorphous metal coatings according to claim 1, characterised in that the metal alloys have the general formula:

            Nia Fea' Crb Zrc Bd M e M' f X g I h     (III)

    in which 3 < a + a' ≤ 85% at.,
    the other symbols having the same meanings as in formula (I).
  4. Wear-resistant and corrosion-resistant amorphous metal coatings according to claim 1, characterised in that the metal alloys have the general formula:

            Nia Coa" Crb Zrc Bd M e M' f X g I h     (IV)

    in which 3 < a + a" ≤ 85% at., the other symbols having the same meanings as in formula (I).
  5. Wear-resistant and corrosion-resistant amorphous metal coatings according to claim 1, characterised in that the metal alloys have the general formula:

            Nia Fea' Coa" Crb Zrc Bd M e M' f X g I h     (V)

    where: 3 < a + a' + a" ≤ 85% at.,
    the other symbols having the same meanings as in formula (I).
  6. A process for obtaining wear-resistant and corrosion-resistant amorphous metal coatings on a substrate according to any one of claims 1 to 5 characterised in that the said coatings are provided by the deposition of metal alloy powders obtained by spraying with a particle size between 20 and 150 µm on a substrate which has been designed to receive them.
  7. A process for obtaining wear-resistant and corrosion-resistant amorphous metal coatings according to claim 6, characterised in that the powders are deposited by thermal projection onto metal substrates in a thickness between 0.03 and 1.5 mm and preferably greater than 0.3 mm.
  8. A process for obtaining wear-resistant and corrosion-resistant amorphous metal coatings according to claim 7, characterised in that powder deposition is performed by the blown plasma arc method with a controlled atmosphere and temperature.
  9. A process for obtaining wear-resistant and corrosion-resistant amorphous metal coatings according to claim 7, characterised in that powder deposition is achieved by the blown plasma arc method, the path of the fused particles being protected from oxidation by an annular jet of nitrogen which is concentric with the plasma jet carrying the particles and of very slightly larger dimensions.
  10. A process for obtaining wear-resistant and corrosion-resistant amorphous metal coatings according to any one of claims 7 to 9, characterised in that powder deposition is followed by a stage of cryogenic cooling.
  11. A process for obtaining wear-resistant and corrosion-resistant amorphous metal coatings according to any one of claims 7 to 10, characterised in that a compacting stage follows deposition of the powdered materials onto substrates by thermal spraying.
  12. A process for obtaining wear-resistant and corrosion-resistant amorphous metal coatings according to any one of claims 6 to 12, characterised in that the powders are deposited onto surfaces of area which may be greater than 1 m.
  13. The application of wear-resistant and corrosion-resistant amorphous metal coatings obtained by means of a process according to any one of claims 6 to 13 for the making of hydraulic machine parts which are resistant to wear due to scraping, cavitation erosion and abrasion at temperatures below 400°C.
EP93420202A 1992-05-22 1993-05-18 Metallic coatings consisting of amorphous wear- and corrosion resistant alloys, process for obtaining these alloys and use as wear resistant coatings of hydraulic material Expired - Lifetime EP0576366B1 (en)

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