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WO2009083483A1 - Coating alloy obtained by powder spraying - Google Patents

Coating alloy obtained by powder spraying Download PDF

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Publication number
WO2009083483A1
WO2009083483A1 PCT/EP2008/067942 EP2008067942W WO2009083483A1 WO 2009083483 A1 WO2009083483 A1 WO 2009083483A1 EP 2008067942 W EP2008067942 W EP 2008067942W WO 2009083483 A1 WO2009083483 A1 WO 2009083483A1
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WO
WIPO (PCT)
Prior art keywords
powder
coating
substrate
aluminum
zinc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2008/067942
Other languages
French (fr)
Inventor
Xavier Vandeneynde
Michel Bordignon
Maïwenn LARNICOL
Jean Crahay
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre de Recherches Metallurgiques CRM ASBL
Original Assignee
Centre de Recherches Metallurgiques CRM ASBL
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre de Recherches Metallurgiques CRM ASBL filed Critical Centre de Recherches Metallurgiques CRM ASBL
Publication of WO2009083483A1 publication Critical patent/WO2009083483A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/261—After-treatment in a gas atmosphere, e.g. inert or reducing atmosphere
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/265—After-treatment by applying solid particles to the molten coating
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C23C24/106—Coating with metal alloys or metal elements only
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate

Definitions

  • the object of the present invention is to obtain a metal substrate having a zinc-based coating whose corrosion resistance is improved, more particularly by adding magnesium in this coating.
  • Magnesium is indeed well known to greatly improve the corrosion resistance.
  • Today alloys Zn-Al-Mg type are deposited by PVD (physical vapor deposition) or by immersion in a bath.
  • Various coatings have thus been patented and are in particular known under the trade names Superdyma ® (Zn, 10% Al, 3% Mg, 0.2% Si), ZAM for Zinc-Aluminum-Magnesium (Zn, 6% A1, 3% Mg) or Magizinc TM (Zn, 1% A1, 1% Mg), etc.
  • These alloys containing magnesium are however fragile and crack during deformation of the substrate.
  • coating processes consist in depositing powders on a substrate by passing through a fluidized bed or by spraying.
  • the substrate from the hot rolling passes into a fluidized bed containing metal particles or alloy having a low melting point, so that the fluidized particles melt in contact with the substrate.
  • the powder is sprayed on a cold substrate and then the substrate undergoes heat treatment to melt the powder.
  • the substrate is electrostatically charged and preheated to a temperature below the melting temperature of the powder which is deposited by passing the substrate in a fluidized bed. Subsequently, the substrate is heat treated to melt the powder.
  • the patent application JP 02 093053 A discloses a spraying process of a Zn-Mg atomized powder on a liquid Zn layer at the outlet of the Zn bath, the substrate being a steel sheet.
  • the application EP 0 769 567 A1 discloses a sheet coating process in which a powder is sprayed onto a metal layer when it is at least partially in the liquid state.
  • the invention aims to provide a metal substrate coating that overcomes the disadvantages of the state of the art.
  • the invention aims to incorporate, in the alloy constituting this coating, magnesium to essentially improve the corrosion resistance while maintaining the resistance to cracking and facilitating the deposition means .
  • the invention aims to flexibly modify the chemical composition of the coating layer.
  • Other properties of the final coating are also referred to as a better resistance to abrasion, an aesthetic appearance or a better attachment of a future organic coating.
  • a first object of the present invention relates to a method of coating a metal substrate by depositing a metal powder characterized in that said powder is composed of a mixture or a an alloy of zinc, aluminum, magnesium with, by weight, 0.1 to 15% aluminum, 0.1 to 50% magnesium and optionally max. 0.2% silicon, and in that, at the time of deposition, said substrate is brought to a temperature higher than the lowest liquidus temperature of the chemical elements and their alloys constituting the powder, so that said powder can at least partially melt in contact with the substrate.
  • a second object of the present invention relates to a metallurgical product coated length or flat obtained by implementing the method described above, in the case where the deposit of powder is produced on a "solid" surface, comprising a first ductile coating based on zinc or zinc / aluminum and a second alloy coating comprising zinc, aluminum and magnesium, said first and second coating having a total thickness of between 15 and 80 ⁇ m for a long product and between 3 and 40 ⁇ m for a flat product.
  • a third object of the present invention relates to a metallurgical product coated lengthwise or flat obtained by implementing the method described above, in the case where the powder deposit is performed on "liquid" surface comprising a magnesium - enriched upper layer and an aluminum - enriched iron - zinc intermetallic lower layer, said alloy coating having a thickness of between 1 and 80 ⁇ m.
  • Figure 1 shows schematically a powder deposition installation per fluidized bed on a wire at the outlet of a zinc bath, according to the present invention.
  • Figure 2 shows a micrographic section obtained on a steel wire before (bottom view) and after (top view) the projection of a zinc powder rich in magnesium and aluminum according to the present invention.
  • the reference sign 1 represents the steel, the sign 2 the intermetallic layer and the sign 3 the coating.
  • the present invention consists in producing a metal powder deposit, containing magnesium, on a metal substrate, coated or not.
  • the powder used according to the invention is typically composed of a zinc alloy containing aluminum (0.1 to 15%, by weight) with a large amount of magnesium (0.1 to 50%, typically 2-8%, by weight). Silicon can also be added to limit the reactivity of the powder with the substrate (max 0.2%, by weight).
  • the following alloying elements may also be included: lithium, bismuth, tin, titanium, copper, nickel, chromium, manganese, molybdenum, tungsten, tantalum, zirconium, lanthanum, cerium, strontium, boron, calcium, vanandium, etc.
  • the powder according to the invention can be prepared by atomization, mechanosynthesis or any other suitable technique. According to preferred embodiments of the invention, this powder is sprayed with a carrier gas at a speed preferably between 1 and 250 m / s, is electrostatically charged or not or is deposited, either by placing ( "batch" line), either by scrolling
  • the metal substrate for receiving the powder according to the invention may be in any conventional form such as for example a wire, a strip or a profiled piece such as a beam or a sheet pile.
  • This metal substrate which may be steel, copper, brass, aluminum, etc., may be pre-coated or not. zinc, aluminum or a zinc / aluminum alloy for example.
  • This pre-coating may be liquid or solid depending on the final type of targeted coating. Indeed, if the powder has a lower melting point than the pre-deposit, the powder projection can produce a very thin second coating
  • the advantage of this process is to deposit a magnesium-rich layer, known for its fragility, on a ductile coating based on zinc or zinc / aluminum.
  • the final coating can thus have excellent deformation and stamping capabilities, because the microcracks obtained on the final coating will be invisible to the naked eye and therefore not impeding the quality criteria required for the final coating. parts of visible aspect.
  • FIG. 2 shows, for example, a micrographic section obtained on a wire 1 before (bottom view) and after (top view) the projection of a zinc powder rich in magnesium (3% by weight) and aluminum (8% by weight). weight). It is clear that a new type of coating has been obtained with a layer richer in magnesium 3 and an intermetallic iron / zinc 2 containing a large amount of aluminum.
  • the powder will preferably be unheated. It may, however, be preheated, preferably in a controlled atmosphere, below its melting point to improve the final quality of the coating. Similarly, the atmosphere around the projection area of the powder can be controlled for example to limit the oxidation of the coating and / or powder.
  • Another advantage of the process according to the invention is that it has a great flexibility of application without need, as in the state of the art, to control the composition and the temperature of the liquid metal coating bath. soaked, as well as holding all the equipment submerged.
  • Another original application of the method according to the invention is to create successive layers in number at least greater than two, in particular lubricating surface layers for forming the substrate.
  • Another original application of the method according to the invention also consists in depositing on each side of the substrate a coating of different composition. The coating obtained after the powder projection may undergo a heat treatment and possibly a melting to modify the properties (structure, roughness, gloss, etc.).
  • the metal powders mainly based on Zn, Al, Mg may be combined with other powders of the carbide or oxide type to increase the hardness of the final coating, to modify its appearance (gloss, etc.) or its properties. hanging of a future organic coating.
  • the particle size of the powders may be quite large (between 1 ⁇ m and 100 ⁇ m) depending on the thickness of the final coating.
  • the powder to be deposited will preferably have Always the largest particle size possible to reduce the cost of manufacturing and improve the quality of the final product. Indeed, since the magnesium-containing powders are always covered with an oxide, it is appropriate to minimize the pollution of the final coating by this oxide by choosing the largest possible particle size.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The invention relates to a method for coating a metal substrate by deposition of a metal powder, characterised in that said metal powder includes a zinc, aluminium and magnesium mixture or alloy with 0.1 to 15 wt % of aluminium, 0.1 to 50 wt % of magnesium and optionally 0.2 wt % at most of silicon, and in that, during the deposition, the substrate is heated to a temperature higher than the lowest temperature at the liquid state of the chemical elements and alloys thereof that form the powder, so that said powder can melt at least partially when in contact with the substrate.

Description

ALLIAGE DE REVETEMENT OBTENU PAR PROJECTION DE POUDRE COATING ALLOY OBTAINED BY PROJECTION OF POWDER

Objet de l'invention [0001] La présente invention a pour objet l'obtention d'un substrat métallique présentant un revêtement à base de zinc dont la résistance à la corrosion est améliorée, plus particulièrement grâce à un ajout de magnésium dans ce revêtement.Object of the invention [0001] The object of the present invention is to obtain a metal substrate having a zinc-based coating whose corrosion resistance is improved, more particularly by adding magnesium in this coating.

Arrière-plan technologique et état de la technique [0002] De nombreuses études sont actuellement menées pour améliorer la résistance à la corrosion des revêtements de substrats métalliques à base de zinc, plus particulièrement par ajout de magnésium.BACKGROUND AND PRIOR ART [0002] Numerous studies are currently being conducted to improve the corrosion resistance of coatings of zinc-based metal substrates, more particularly by the addition of magnesium.

[0003] Le magnésium est en effet bien connu pour améliorer fortement la résistance à la corrosion. Aujourd'hui des alliages de type Zn-Al-Mg sont déposés par PVD (physical vapor déposition) ou par immersion dans un bain. Différents revêtements ont ainsi été brevetés et sont notamment connus sous des noms commerciaux du type Superdyma® (Zn, 10%Al, 3%Mg, 0,2%Si), ZAM pour Zinc- Aluminium-Magnésium (Zn, 6%A1, 3%Mg) ou Magizinc™ (Zn, 1%A1, l%Mg) , etc. Ces alliages contenant du magnésium sont cependant fragiles et se fissurent lors d'une déformation du substrat.Magnesium is indeed well known to greatly improve the corrosion resistance. Today alloys Zn-Al-Mg type are deposited by PVD (physical vapor deposition) or by immersion in a bath. Various coatings have thus been patented and are in particular known under the trade names Superdyma ® (Zn, 10% Al, 3% Mg, 0.2% Si), ZAM for Zinc-Aluminum-Magnesium (Zn, 6% A1, 3% Mg) or Magizinc ™ (Zn, 1% A1, 1% Mg), etc. These alloys containing magnesium are however fragile and crack during deformation of the substrate.

[0004] D'autres procédés de revêtement consistent à déposer des poudres sur un substrat par passage dans un lit fluidisé ou par pulvérisation. [0005] Dans la demande FR-A-2 354 389, le substrat issu de la chaude de laminage passe dans un lit fluidisé contenant des particules de métal ou d'alliage ayant un point de fusion bas, de sorte que les particules fluidisées fondent au contact du substrat.Other coating processes consist in depositing powders on a substrate by passing through a fluidized bed or by spraying. In the application FR-A-2 354 389, the substrate from the hot rolling passes into a fluidized bed containing metal particles or alloy having a low melting point, so that the fluidized particles melt in contact with the substrate.

[0006] Dans la demande US 2007/240603 Al, la poudre est pulvérisée sur un substrat froid et, ensuite, le substrat subit un traitement thermique afin de fondre la poudre . [0007] Dans la demande WO 94/29030 A, le substrat est chargé électrostatiquement et préchauffé à une température inférieure à la température de fusion de la poudre qui est déposée par passage du substrat dans un lit fluidisé. Ensuite, le substrat subit un traitement thermique afin de fondre la poudre.In the application US 2007/240603 A1, the powder is sprayed on a cold substrate and then the substrate undergoes heat treatment to melt the powder. In the application WO 94/29030 A, the substrate is electrostatically charged and preheated to a temperature below the melting temperature of the powder which is deposited by passing the substrate in a fluidized bed. Subsequently, the substrate is heat treated to melt the powder.

[0008] II est également connu de projeter de la poudre métallique (notamment fer ou fer/zinc, etc.) sur des aciers galvanisés au trempé, notamment destinés au « galvanneal », pour modifier leur revêtement. [0009] La demande de brevet JP 02 093053 A divulgue un procédé de pulvérisation d'une poudre atomisée Zn-Mg sur une couche de Zn liquide en sortie du bain de Zn, le substrat étant une tôle d'acier. [0010] De même, la demande EP 0 769 567 Al présente un procédé de revêtement de tôle dans lequel on projette une poudre sur une couche métallique lorsqu'elle est au- moins partiellement à l'état liquide.It is also known to project metal powder (including iron or iron / zinc, etc.) on steels galvanized dipping, especially for the "galvanneal" to modify their coating. The patent application JP 02 093053 A discloses a spraying process of a Zn-Mg atomized powder on a liquid Zn layer at the outlet of the Zn bath, the substrate being a steel sheet. [0010] Similarly, the application EP 0 769 567 A1 discloses a sheet coating process in which a powder is sprayed onto a metal layer when it is at least partially in the liquid state.

[0011] II est aussi connu de déposer des revêtements à partir de poudres sous forme de gouttelettes (ce qui est appelé « thermal spray ») ou par application au rouleau (KR20010063534, JP2267250, JP2118088, JP58058263, GB1343654, JP10001766, etc.). Buts de l ' inventionIt is also known to deposit coatings from powders in the form of droplets (which is called "thermal spray") or by roller application (KR20010063534, JP2267250, JP2118088, JP58058263, GB1343654, JP10001766, etc.). . Goals of the invention

[0012] L' invention a pour but de fournir un revêtement de substrat métallique qui permette de s'affranchir des inconvénients de l'état de la technique. [0013] En particulier, l'invention a pour but d'incorporer, dans l'alliage constituant ce revêtement, du magnésium pour en améliorer essentiellement la tenue à la corrosion tout en conservant la résistance à la fissuration et en facilitant le moyen de dépôt. De manière plus générale, l'invention vise à modifier de manière flexible la composition chimique de la couche de revêtement. [0014] D'autres propriétés du revêtement final sont aussi visées comme une meilleure tenue à l'abrasion, un aspect esthétique ou un meilleur accrochage d'un futur revêtement organique.The invention aims to provide a metal substrate coating that overcomes the disadvantages of the state of the art. In particular, the invention aims to incorporate, in the alloy constituting this coating, magnesium to essentially improve the corrosion resistance while maintaining the resistance to cracking and facilitating the deposition means . More generally, the invention aims to flexibly modify the chemical composition of the coating layer. Other properties of the final coating are also referred to as a better resistance to abrasion, an aesthetic appearance or a better attachment of a future organic coating.

Résumé de l ' inventionSummary of the invention

[0015] Un premier objet de la présente invention, indiqué dans la revendication 1, se rapporte à un procédé de revêtement d'un substrat métallique par dépôt d'une poudre métallique caractérisé en ce que ladite poudre est composée d'un mélange ou d'un alliage de zinc, aluminium, magnésium avec, en poids, 0,1 à 15% d'aluminium, 0,1 à 50% de magnésium et optionnellement max . 0,2% de silicium, et en ce que, au moment du dépôt, ledit substrat est porté à une température supérieure à la plus basse des températures de liquidus des éléments chimiques et de leurs alliages composant la poudre, de sorte que ladite poudre puisse entrer en fusion au moins partiellement lors du contact avec le substrat.A first object of the present invention, indicated in claim 1, relates to a method of coating a metal substrate by depositing a metal powder characterized in that said powder is composed of a mixture or a an alloy of zinc, aluminum, magnesium with, by weight, 0.1 to 15% aluminum, 0.1 to 50% magnesium and optionally max. 0.2% silicon, and in that, at the time of deposition, said substrate is brought to a temperature higher than the lowest liquidus temperature of the chemical elements and their alloys constituting the powder, so that said powder can at least partially melt in contact with the substrate.

[0016] Un deuxième objet de la présente invention, indiqué dans la revendication 20, se rapporte à un produit métallurgique long ou plat revêtu obtenu par mise en œuvre du procédé décrit ci-dessus, dans le cas où le dépôt de poudre est réalisé sur surface « solide », comprenant un premier revêtement ductile à base de zinc ou zinc/aluminium et un second revêtement allié comportant du zinc, de l'aluminium et du magnésium, ledit premier et second revêtement ayant une épaisseur totale comprise entre 15 et 80μm pour un produit long et entre 3 et 40μm pour un produit plat.A second object of the present invention, indicated in claim 20, relates to a metallurgical product coated length or flat obtained by implementing the method described above, in the case where the deposit of powder is produced on a "solid" surface, comprising a first ductile coating based on zinc or zinc / aluminum and a second alloy coating comprising zinc, aluminum and magnesium, said first and second coating having a total thickness of between 15 and 80μm for a long product and between 3 and 40μm for a flat product.

[0017] Un troisième objet de la présente invention, indiqué dans la revendication 21, se rapporte à un produit métallurgique long ou plat revêtu obtenu par mise en œuvre du procédé décrit ci-dessus, dans le cas où le dépôt de poudre est réalisé sur surface « liquide », comportant une couche supérieure enrichie en magnésium et une couche inférieure d' intermétallique fer/zinc enrichie en aluminium, ledit revêtement allié ayant une épaisseur comprise entre 1 et 80μm.A third object of the present invention, indicated in claim 21, relates to a metallurgical product coated lengthwise or flat obtained by implementing the method described above, in the case where the powder deposit is performed on "liquid" surface comprising a magnesium - enriched upper layer and an aluminum - enriched iron - zinc intermetallic lower layer, said alloy coating having a thickness of between 1 and 80 μm.

[0018] Des modes d'exécution particuliers de l'invention sont décrits dans les revendications 2 à 19, ou sous toute autre forme combinant les caractéristiques additionnelles de ces revendications.Particular embodiments of the invention are described in claims 2 to 19, or in any other form combining the additional features of these claims.

Brève description des figuresBrief description of the figures

[0019] La figure 1 représente schématiquement une installation de dépôt de poudre par lit fluidisé sur un fil à la sortie d'un bain de zinc, selon la présente invention. [0020] La figure 2 représente une coupe micrographique obtenue sur un fil d'acier avant (vue du bas) et après (vue du haut) la projection d'une poudre de zinc riche en magnésium et aluminium selon la présente invention. Sur la figure 2, le signe de référence 1 représente l'acier, le signe 2 la couche d' intermétallique et le signe 3 le revêtement. Description détaillée de l ' invention[0019] Figure 1 shows schematically a powder deposition installation per fluidized bed on a wire at the outlet of a zinc bath, according to the present invention. Figure 2 shows a micrographic section obtained on a steel wire before (bottom view) and after (top view) the projection of a zinc powder rich in magnesium and aluminum according to the present invention. In FIG. 2, the reference sign 1 represents the steel, the sign 2 the intermetallic layer and the sign 3 the coating. Detailed description of the invention

[0021] La présente invention consiste à réaliser un dépôt de poudre métallique, contenant du magnésium, sur un substrat métallique, revêtu ou non. [0022] La poudre utilisée selon l'invention est typiquement composée d'un alliage de zinc contenant de l'aluminium (0,1 à 15 %, en poids) avec une quantité importante de magnésium (0,1 à 50%, typiquement 2 à 8%, en poids). Le silicium peut également être ajouté pour limiter la réactivité de la poudre avec le substrat (max 0.2%, en poids) . Peuvent également être inclus les éléments d'alliage suivants : lithium, bismuth, étain, titane, cuivre, nickel, chrome, manganèse, molybdène, tungstène, tantale, zirconium, lanthane, cérium, strontium, bore, calcium, vanandium, etc.The present invention consists in producing a metal powder deposit, containing magnesium, on a metal substrate, coated or not. The powder used according to the invention is typically composed of a zinc alloy containing aluminum (0.1 to 15%, by weight) with a large amount of magnesium (0.1 to 50%, typically 2-8%, by weight). Silicon can also be added to limit the reactivity of the powder with the substrate (max 0.2%, by weight). The following alloying elements may also be included: lithium, bismuth, tin, titanium, copper, nickel, chromium, manganese, molybdenum, tungsten, tantalum, zirconium, lanthanum, cerium, strontium, boron, calcium, vanandium, etc.

[0023] La poudre selon l'invention peut être préparée par atomisation, mécanosynthèse ou toute autre technique appropriée. [0024] Selon des formes préférées d'exécution de l'invention, cette poudre est projetée par un gaz porteur à une vitesse comprise de préférence entre 1 et 250 m/s, est chargée électrostatiquement ou non ou est déposée, soit en plaçant (ligne de type « batch ») , soit en faisant défilerThe powder according to the invention can be prepared by atomization, mechanosynthesis or any other suitable technique. According to preferred embodiments of the invention, this powder is sprayed with a carrier gas at a speed preferably between 1 and 250 m / s, is electrostatically charged or not or is deposited, either by placing ( "batch" line), either by scrolling

(ligne de type « continu ») le substrat dans un lit fluidisé. Un exemple d'installation de dépôt de poudre à lit fluidisé selon la présente invention est représenté sur la figure 1.("Continuous" type line) the substrate in a fluidized bed. An example of a fluidized bed powder deposition installation according to the present invention is shown in FIG.

[0025] Le substrat métallique destiné à recevoir la poudre selon l'invention peut se présenter sous toute forme usuelle telle que par exemple un fil, une bande ou encore une pièce profilée comme une poutrelle ou une palplanche. Ce substrat métallique, qui peut être en acier, cuivre, laiton, aluminium, etc., peut être pré-revêtu ou non de zinc, d'aluminium ou d'un alliage zinc/aluminium par exemple .The metal substrate for receiving the powder according to the invention may be in any conventional form such as for example a wire, a strip or a profiled piece such as a beam or a sheet pile. This metal substrate, which may be steel, copper, brass, aluminum, etc., may be pre-coated or not. zinc, aluminum or a zinc / aluminum alloy for example.

[0026] Ce pré-revêtement pourra être liquide ou solide en fonction du type final de revêtement visé. [0027] En effet, si la poudre a un point de fusion inférieure à celle du pré-dépôt, la projection de poudre pourra produire un second revêtement très minceThis pre-coating may be liquid or solid depending on the final type of targeted coating. Indeed, if the powder has a lower melting point than the pre-deposit, the powder projection can produce a very thin second coating

(typiquement < lOμm) mais très riche en magnésium sur un revêtement solide. L'avantage de ce procédé est de déposer une couche riche en magnésium, connue pour sa fragilité, sur un revêtement ductile à base de zinc ou zinc/aluminium. Le revêtement final pourra ainsi avoir d'excellentes aptitudes à la déformation et à l'emboutissage, car les microfissures obtenues sur le revêtement final seront invisibles à l'œil nu et donc non gênantes vis-à-vis des critères de qualité requis pour des pièces d'aspect visible .(typically <10μm) but very rich in magnesium on a solid coating. The advantage of this process is to deposit a magnesium-rich layer, known for its fragility, on a ductile coating based on zinc or zinc / aluminum. The final coating can thus have excellent deformation and stamping capabilities, because the microcracks obtained on the final coating will be invisible to the naked eye and therefore not impeding the quality criteria required for the final coating. parts of visible aspect.

[0028] Si la poudre est projetée sur un revêtement liquide, une modification du premier revêtement sera obtenue. La figure 2 montre par exemple une coupe micrographique obtenue sur un fil 1 avant (vue du bas) et après (vue du haut) la projection d'une poudre de zinc riche en magnésium (3% en poids) et aluminium (8% en poids). Il apparaît clairement qu'un nouveau type de revêtement a été obtenu avec une couche plus riche en magnésium 3 et un intermétallique fer/zinc 2 contenant une grande quantité d'aluminium.If the powder is sprayed onto a liquid coating, a modification of the first coating will be obtained. FIG. 2 shows, for example, a micrographic section obtained on a wire 1 before (bottom view) and after (top view) the projection of a zinc powder rich in magnesium (3% by weight) and aluminum (8% by weight). weight). It is clear that a new type of coating has been obtained with a layer richer in magnesium 3 and an intermetallic iron / zinc 2 containing a large amount of aluminum.

[0029] Selon une forme d'exécution, la poudre sera de préférence non chauffée. Elle pourra cependant être préchauffée, de préférence sous atmosphère contrôlée, en dessous de son point de fusion pour améliorer la qualité finale du revêtement. De même, l'atmosphère autour de l'endroit de projection de la poudre pourra être contrôlée par exemple afin de limiter l'oxydation du revêtement et/ou de la poudre.According to one embodiment, the powder will preferably be unheated. It may, however, be preheated, preferably in a controlled atmosphere, below its melting point to improve the final quality of the coating. Similarly, the atmosphere around the projection area of the powder can be controlled for example to limit the oxidation of the coating and / or powder.

[0030] Un autre avantage du procédé selon l'invention est qu'il présente une grande souplesse d'application sans nécessité, comme dans l'état de la technique, de contrôler la composition et la température du bain de métal liquide de revêtement au trempé, ainsi que la tenue de tous les équipements immergés. [0031] Une autre application originale du procédé selon l'invention consiste à créer des couches successives en nombre au moins supérieur à deux, en particulier des couches superficielles lubrifiantes pour la mise à forme du substrat . [0032] Une autre application originale du procédé selon l'invention consiste également à déposer sur chaque face du substrat un revêtement de composition différente. [0033] Le revêtement obtenu après la projection de poudre pourra subir un traitement thermique et éventuellement une fusion pour en modifier les propriétés (structure, rugosité, brillance, etc.). Il pourra également subir un « skin-pass » (dans le cas d'une tôle) ou un tréfilage pour y imposer une rugosité déterminée, apte à recevoir d'autres revêtements du type organique (peinture, ...) ou pour améliorer l'adhérence de la poudre. [0034] Les poudres métalliques principalement à base de Zn, Al, Mg pourront être associées à d'autres poudres du type carbure ou oxyde pour augmenter la dureté du revêtement final, pour modifier son aspect (brillance, etc.) ou ses propriétés d'accrochage d'un futur revêtement organique.Another advantage of the process according to the invention is that it has a great flexibility of application without need, as in the state of the art, to control the composition and the temperature of the liquid metal coating bath. soaked, as well as holding all the equipment submerged. Another original application of the method according to the invention is to create successive layers in number at least greater than two, in particular lubricating surface layers for forming the substrate. Another original application of the method according to the invention also consists in depositing on each side of the substrate a coating of different composition. The coating obtained after the powder projection may undergo a heat treatment and possibly a melting to modify the properties (structure, roughness, gloss, etc.). It may also undergo a "skin pass" (in the case of a sheet) or wire drawing to impose a specific roughness, able to receive other coatings of the organic type (paint, ...) or to improve the adhesion of the powder. The metal powders mainly based on Zn, Al, Mg may be combined with other powders of the carbide or oxide type to increase the hardness of the final coating, to modify its appearance (gloss, etc.) or its properties. hanging of a future organic coating.

[0035] La granulométrie des poudres pourra être assez étendue (entre lμm et lOOμm) en fonction de l'épaisseur du revêtement final. Toutefois, selon l'invention, la poudre à déposer, aura de préférence toujours la plus grande granulométrie possible pour diminuer son coût de fabrication et améliorer la qualité du produit final. En effet, comme les poudres contenant du magnésium sont toujours recouvertes d'un oxyde, il convient de minimiser la pollution du revêtement final par cet oxyde en choisissant la plus grande taille possible de particule. The particle size of the powders may be quite large (between 1 μm and 100 μm) depending on the thickness of the final coating. However, according to the invention, the powder to be deposited will preferably have Always the largest particle size possible to reduce the cost of manufacturing and improve the quality of the final product. Indeed, since the magnesium-containing powders are always covered with an oxide, it is appropriate to minimize the pollution of the final coating by this oxide by choosing the largest possible particle size.

Claims

REVENDICATIONS 1. Procédé de revêtement d'un substrat métallique par dépôt d'une poudre métallique caractérisé en ce que ladite poudre est composée d'un mélange ou d'un alliage de zinc, aluminium, magnésium avec, en poids, 0,1 à 15% d'aluminium, 0,1 à 50% de magnésium et optionnellement max . 0,2% de silicium, et en ce que, au moment du dépôt, ledit substrat est porté à une température supérieure à la plus basse des températures de liquidus des éléments chimiques et de leurs alliages composant la poudre, de sorte que ladite poudre puisse entrer en fusion au moins partiellement lors du contact avec le substrat.1. A method of coating a metal substrate by deposition of a metal powder characterized in that said powder is composed of a mixture or alloy of zinc, aluminum, magnesium with, by weight, 0.1 to 15 % aluminum, 0.1 to 50% magnesium and optionally max. 0.2% silicon, and in that, at the time of deposition, said substrate is brought to a temperature higher than the lowest liquidus temperature of the chemical elements and their alloys constituting the powder, so that said powder can at least partially melt in contact with the substrate. 2. Procédé selon la revendication 1, caractérisé en ce que la poudre comprend en outre un des éléments constitués par le lithium, le bismuth, le cuivre, le nickel, le chrome, le manganèse, le molybdène, l'étain, le titane, le tungstène, le tantale, le lanthane, le cérium, le strontium, le bore, le calcium, le vanadium ou le zirconium.2. Method according to claim 1, characterized in that the powder further comprises one of the elements consisting of lithium, bismuth, copper, nickel, chromium, manganese, molybdenum, tin, titanium, tungsten, tantalum, lanthanum, cerium, strontium, boron, calcium, vanadium or zirconium. 3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la poudre est obtenue par mécanosynthèse (mechanical alloying) ou par atomisation.3. Method according to claim 1 or 2, characterized in that the powder is obtained by mechanosynthesis (mechanical alloying) or by atomization. 4. Procédé selon la revendication 1, caractérisé en ce que le substrat métallique comprend un fil, une bande ou une pièce profilée comme une poutrelle ou une palplanche .4. Method according to claim 1, characterized in that the metal substrate comprises a wire, a strip or a profiled piece such as a beam or a sheet pile. 5. Procédé selon la revendication 4, caractérisé en ce que le substrat métallique est en acier, cuivre, laiton ou aluminium.5. Method according to claim 4, characterized in that the metal substrate is steel, copper, brass or aluminum. 6. Procédé selon la revendication 4 ou 5, caractérisé en ce que le substrat métallique est prérevêtu, de préférence de zinc, d'aluminium ou d'un alliage zinc/aluminium. 6. Method according to claim 4 or 5, characterized in that the metal substrate is pre-coated, preferably zinc, aluminum or a zinc / aluminum alloy. 7. Procédé selon la revendication 2 ou 3, caractérisé en ce que la poudre précitée est enrobée ou associée à d'autres poudres du type carbure ou oxyde.7. Method according to claim 2 or 3, characterized in that the aforementioned powder is coated or associated with other powders of the carbide or oxide type. 8. Procédé selon la revendication 1 caractérisé en ce que la poudre comporte 2 à 8% en poids de magnésium.8. The method of claim 1 characterized in that the powder comprises 2 to 8% by weight of magnesium. 9. Procédé selon la revendication 1, caractérisée en ce que la granulométrie de la poudre est comprise entre lμm et lOOμm.9. The method of claim 1, characterized in that the particle size of the powder is between 1 .mu.m and lOOμm. 10. Procédé selon la revendication 1, caractérisé en ce que la poudre est projetée sur le substrat par un gaz porteur à une vitesse comprise entre 1 et 250 m/s.10. The method of claim 1, characterized in that the powder is projected onto the substrate by a carrier gas at a speed between 1 and 250 m / s. 11. Procédé selon la revendication 1, caractérisée en ce que la poudre est chargée électrostatiquement . 11. The method of claim 1, characterized in that the powder is electrostatically charged. 12. Procédé selon la revendication 1, caractérisée en ce que la poudre est déposée, soit en plaçant, soit en faisant défiler le substrat dans un lit fluidisé .12. The method of claim 1, characterized in that the powder is deposited, either by placing or by scrolling the substrate in a fluidized bed. 13. Procédé selon la revendication 1, caractérisé en ce que la poudre est préchauffée à une température située en dessous de son point de fusion, de préférence sous atmosphère contrôlée.13. The method of claim 1, characterized in that the powder is preheated to a temperature below its melting point, preferably in a controlled atmosphere. 14. Procédé selon la revendication 1, caractérisé en ce que l'atmosphère autour de l'endroit de dépôt de la poudre sur le substrat est contrôlée de manière à limiter l'oxydation du revêtement et/ou de la poudre.14. The method of claim 1, characterized in that the atmosphere around the place of deposition of the powder on the substrate is controlled so as to limit the oxidation of the coating and / or powder. 15. Procédé selon la revendication 1, caractérisé en ce que, par dépôts successifs de poudre, on crée des couches successives correspondantes en nombre au moins supérieur à deux, dont en particulier au moins une couche superficielle lubrifiante pour la mise à forme du substrat.15. The method of claim 1, characterized in that, by successive deposition of powder, is created successive layers corresponding in number at least greater than two, including in particular at least one lubricating surface layer for forming the substrate. 16. Procédé selon la revendication 1, caractérisé en ce que, après le dépôt de poudre, le revêtement obtenu peut subir un traitement thermique, une fusion, un tréfilage et/ou un « skin-pass ».16. Process according to claim 1, characterized in that, after the deposition of powder, the coating obtained may undergo heat treatment, fusion, wire drawing and / or skin-pass. 17. Procédé selon la revendication 6, caractérisé en ce que le prérevêtement est obtenu par trempé dans un bain de métal fondu ou par électrozinguage .17. The method of claim 6, characterized in that the precoat is obtained by dipping in a bath of molten metal or by electrozinguage. 18. Procédé selon l'une quelconque des revendications 6 à 17, caractérisé en ce que le prérevêtement du substrat est solide au moment du dépôt de la poudre, c'est-à-dire que la température du substrat est inférieure à la température de fusion du prérevêtement, de manière à créer avec la fusion de la poudre une couche de revêtement distincte de la couche de prérevêtement.18. Method according to any one of claims 6 to 17, characterized in that the pre-coating of the substrate is solid at the time of deposition of the powder, that is to say that the substrate temperature is below the temperature of the substrate. merging the precoat, so as to create with the melting of the powder a coating layer distinct from the pre-coating layer. 19. Procédé selon l'une quelconque des revendications 6 à 17, caractérisé en ce que le prérevêtement du substrat est au moins partiellement liquide au moment du dépôt de la poudre, de manière à modifier la composition chimique de la couche de revêtement finale .19. Method according to any one of claims 6 to 17, characterized in that the pre-coating of the substrate is at least partially liquid at the time of deposition of the powder, so as to modify the chemical composition of the final coating layer. 20. Produit métallurgique long ou plat revêtu obtenu par mise en œuvre du procédé selon la revendication20. Long metallurgical product or coated flat obtained by implementing the method according to the claim 18, comprenant un premier revêtement ductile à base de zinc ou zinc/aluminium et un second revêtement allié comportant du zinc, de l'aluminium et du magnésium, ledit premier et second revêtement ayant une épaisseur totale comprise entre 15 et 80μm pour un produit long et entre 3 et 40μm pour un produit plat.18, comprising a first ductile coating based on zinc or zinc / aluminum and a second alloy coating comprising zinc, aluminum and magnesium, said first and second coating having a total thickness between 15 and 80μm for a long product. and between 3 and 40μm for a flat product. 21. Produit métallurgique long ou plat revêtu obtenu par mise en œuvre du procédé selon la revendication21. Long metallurgical product or coated flat obtained by implementing the process according to claim 19, comprenant un revêtement allié comportant une couche supérieure enrichie en magnésium et une couche inférieure d' intermétallique fer/zinc enrichie en aluminium, ledit revêtement allié ayant une épaisseur comprise entre 1 et 80μm. 19, comprising an alloy coating comprising a magnesium-enriched upper layer and an aluminum-enriched iron-zinc intermetallic lower layer, said alloy coating having a thickness of between 1 and 80 μm.
PCT/EP2008/067942 2007-12-20 2008-12-18 Coating alloy obtained by powder spraying Ceased WO2009083483A1 (en)

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