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EP1527208A2 - Method for coating the surface of metallic material, device for carrying out said method - Google Patents

Method for coating the surface of metallic material, device for carrying out said method

Info

Publication number
EP1527208A2
EP1527208A2 EP03758204A EP03758204A EP1527208A2 EP 1527208 A2 EP1527208 A2 EP 1527208A2 EP 03758204 A EP03758204 A EP 03758204A EP 03758204 A EP03758204 A EP 03758204A EP 1527208 A2 EP1527208 A2 EP 1527208A2
Authority
EP
European Patent Office
Prior art keywords
coating
metal
strip
metallic material
layer
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.)
Withdrawn
Application number
EP03758204A
Other languages
German (de)
French (fr)
Inventor
Patrick Choquet
Daniel Chaleix
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.)
ArcelorMittal France SA
Original Assignee
USINOR SA
Arcelor France SA
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 USINOR SA, Arcelor France SA filed Critical USINOR SA
Publication of EP1527208A2 publication Critical patent/EP1527208A2/en
Withdrawn legal-status Critical Current

Links

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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer

Definitions

  • the invention relates to the coating of metal surfaces. More specifically, it relates to treatments for coating the surface of a metallic material intended to give it a three-dimensional visual effect.
  • a visual effect can be obtained with holograms, which are obtained by recording and reproducing an image using two laser beams on a photosensitive support capable of recording light interference of good contrast.
  • supports are, for example, thermoplastic films, photopolymers, photosensitive films ...
  • the decoration of metallic packaging in steel or aluminum is a privileged use of this technique, which has the disadvantage, for the metallurgical enterprise, of requiring the intervention of an external supplier who delivers the photosensitive support to it.
  • the support is liable to become detached from the packaging or to be damaged during the treatments and manipulations undergone by said packaging after bonding or co-laminating.
  • the object of the invention is to propose a method making it possible to obtain three-dimensional visual effects on the surface of a metallic material without having recourse to the application to this surface of a photosensitive support.
  • the subject of the invention is a method of coating the surface of a metallic material having a crystallographic structure, according to which a first coating of said material is carried out with a layer of a metal or of a metallic alloy with melting point equal to T f , of thickness less than or equal to 2.5 ⁇ m, characterized in that:
  • a heat treatment is carried out on said first coating by a rapid heating means so as to bring the surface of said first coating to a temperature between 0.8T f and T f ;
  • a second coating is deposited from a metal or a metal alloy, of thickness less than or equal to 1 ⁇ m.
  • said first and second coatings have melting points less than or equal to 700 ° C.
  • Said first and second coatings can be made of the same material.
  • the deposition on said second coating is then carried out of a transparent mineral film.
  • Said metallic material to be coated may preferably be carbon steel, stainless steel, or aluminum or one of its alloys.
  • Said first coating can preferably be produced by electrodeposition or by a vacuum deposition process.
  • Said rapid heating means may preferably be an infrared heating device, an induction heating device, a plasma effluvium device with a non-reactive gas or an ion bombardment with a non-reactive gas .
  • Said second coating can preferably be produced by electrodeposition or by a vacuum deposition process.
  • Said transparent mineral film can be deposited by a reactive plasma deposition process.
  • Said first and second coatings can each consist of tin and / or aluminum.
  • Said mineral film can consist of a metal oxide or a mixture of metal oxides, preferably chosen from oxides of austenitic stainless steel, chromium, titanium, silicon, zinc, tin.
  • the metallic material can be in the form of a moving strip, and the various stages of the process can be carried out continuously by means of installations arranged successively on the path of the moving strip.
  • the invention also relates to a device for coating a metallic material in the form of a strip, characterized in that it comprises means for scrolling said strip and, successively arranged on the path of said strip:
  • the device may comprise, following said second means for coating said strip with a layer of a metal or a metal alloy, means for coating said strip with a transparent mineral film.
  • the invention also relates to a metallic material, characterized in that it comprises on at least one of its surfaces a metallic coating with a three-dimensional visual effect, said coating being formed directly on said surface of the material, and produced in particular by the previous process.
  • the invention consists in obtaining the three-dimensional visual effect sought by a series of surface treatments of the metallic material itself.
  • a multilayer coating is thus obtained which cannot be detached from the metallic material and can be produced by the metallurgical company which manufactured the basic material.
  • This coating in addition to its aesthetic qualities, has many technical advantages, and allows the manufacturer of the metallic material to retain complete control of the decoration process.
  • FIGS. 1 to 6 show the aspects of different coatings obtained by various variants of the method according to the invention.
  • the starting material is a metallic material, such as carbon steel, stainless steel, aluminum or an alloy thereof, etc. It is for example in the form of a plate or a wound strip. In the latter case, it is possible to carry out the treatment which will be described by unwinding the strip and scrolling it continuously in an installation where the apparatuses making it possible to carry out the different stages of the treatment are arranged one after the other. on the path of the strip. In order for the desired aesthetic effect to be obtained, the metallic material used as a substrate must have a crystallographic structure.
  • the first process step is the deposition of a first coating, comprising a metallic member (aluminum or tin, for example) or a metal alloy, preferably low-melting point T f of the order of 700 ° C or lower.
  • This coating must have a thickness less than or equal to 2.5 ⁇ m.
  • it is produced by an electrodeposition process, or by a vacuum deposition process.
  • vacuum deposition methods which can be used, mention may be made of the conventionally known methods of vacuum evaporation, magnetron sputtering, ion plating, self-induced ion plating.
  • the second stage of the process is a heat treatment carried out on the first coating, by a rapid heating means, such as infrared lamps, an inductor, a plasma effluvium, or an ion bombardment with a non-reactive gas such as 'a rare gas.
  • a rapid heating means such as infrared lamps, an inductor, a plasma effluvium, or an ion bombardment with a non-reactive gas such as 'a rare gas.
  • This heat treatment must bring the surface of the first coating to a temperature between 0.8 T f and T f .
  • T f be less than or equal to 700 ° C.
  • the third step of the process is the deposition of a second coating, from a metallic element or an alloy identical or not to the material of the first coating.
  • This coating must have a thickness not exceeding 1 ⁇ m. It can be produced by the same methods as the first coating.
  • the method may include a fourth step consisting in depositing on the second metallic coating a transparent mineral film.
  • a transparent mineral film Materials such as oxides of austenitic stainless steel, chromium, titanium, silicon, zinc, tin (non-limiting list) and their mixtures are particularly indicated.
  • This transparent mineral deposition can be carried out by any means known for this purpose, the methods using a reactive plasma deposition being particularly indicated. If this film has a thickness less than or equal to 1 ⁇ m, a colored coating can be obtained by interference effect of the mineral film. Green, yellow, blue, purple and red colors are accessible in this way, depending on the refractive index of the deposited material. In general, this transparent film gives an appearance of additional depth to the three-dimensional appearance patterns obtained following the first three steps of the process.
  • the size of the patterns obtained depends on the amount of energy used during the second step of the process and on the thickness of the coating: the patterns will be all the greater as this amount of energy and / or this thickness will be important.
  • the use, as coating material during the first step of the process, of a metal or alloy with a low melting point (700 ° C. or less) makes it possible to carry out the metallurgical transformation of the coating during the second step in a time very brief.
  • the heating methods which have been mentioned make it possible to provide the necessary energy in a minimum of time.
  • the method according to the invention has several advantages. As we said, it allows the manufacturer of metal products to retain full control of the process.
  • the coating generating the three-dimensional visual effect here being an integral part of the support, there is no risk of it coming off during subsequent treatments and manipulations.
  • the coating thus obtained improves the resistance of the substrate to cosmetic corrosion.
  • the coating is also more resistant to ultraviolet and temperature. It is less sensitive to fingerprints. It has great surface hardness, which makes it less susceptible to scratches. It is easy to clean and is resistant to cleaning products and other mechanical stresses.
  • the coating metal used is suitable (for example tin), to make the coating compatible with food use.
  • the sheet is coated with a 0.8 ⁇ m layer of tin by magnetron sputtering in an argon atmosphere under a pressure of 10 "3 mbar (0.1 Pa).
  • target is 0.9A and the target voltage is 450 V.
  • the tin deposition rate is 0.25 ⁇ m / min.
  • the sheet is heat treated with an argon plasma under a pressure of 10 "3 mbar (0.1 Pa).
  • the energy given to the argon ions is 400 eV and the dose of ions received by the sheet is 4.7.10 22 ArVm 2 ions.
  • the sheet is placed as a cathode.
  • the surface of the tin is brought to a temperature of the order of 210 ° C.
  • a 0.4 ⁇ m tin coating is deposited by magnetron sputtering, under the same experimental conditions as for the first coating.
  • CVD plasma is deposited with a transparent silica film, with a thickness of 0.1 ⁇ m.
  • the deposition is carried out in an atmosphere composed of hexamethyldisiloxane (HMDSO) and oxygen, under a pressure of 10 "3 mbar (0.1 Pa), with a ratio of the partial pressures of HMDSO and O 2 of 1 / 10.
  • a frequency current of 50 kHz is used at a power of 100 W.
  • the deposition rate is 1.0 ⁇ m / min.
  • This coating gives a coating whose external appearance is shown in FIG. 1, having anti-corrosion and anti-fingerprint properties, easy to clean, and having a high surface hardness. It is able to withstand high mechanical, chemical and thermal stresses.
  • a coating of said steel sheet is carried out under conditions identical to those of Example 1 for the first three stages.
  • the fourth step consists in producing a titanium oxide film colored by reactive magnetron sputtering of a titanium target. Its thickness is 0.05 ⁇ m.
  • the conditions for its realization are an O 2 / Ar atmosphere with 0.4, a total pressure of 5.10 "3 mbar (10.5 Pa) and a power of 1.7 kW. This gives a coating represented in FIG.
  • Example 2 having properties similar to that of Example 1, with in plus a blue colored appearance due to the refractive index of titanium oxide (2.5) and the properties specific to titanium oxide, namely great chemical inertness, good resistance to high temperature, good resistance to chemical attack, and a self-cleaning action due to its catalytic effect of degradation of materials containing carbon and oxygen in the presence of ultraviolet light.
  • This mild steel sheet is coated under the same conditions as for Example 2, except that the thickness of the first deposit of tin is increased to 1.2 ⁇ m, as well as the dose of ions received by the first layer of tin during the second step of the process. This dose reaches here 9.4.10 22 Ar " 7m 2 ions. The surface of the tin is brought to a temperature of the order of 235 ° C. The result is visible in FIG. 3.
  • EXAMPLE 4 A coating of said mild steel sheet is carried out under the same conditions as for Example 2, except that, as in Example 3, the dose of ions received by the first layer is increased to 9 , 4.10 22 Ar + ions / m 2 , and increasing the thickness of the titanium oxide film to 0.08 ⁇ m. The result is visible in FIG. 4. It is noted that the increase in energy used during the second stage of the treatment leads to a substantial increase in the size of the patterns.
  • EXAMPLE 5 The said sheet is coated under conditions identical to those of Example 1, except that, for the second step, two infrared lamps are used to heat the substrate and its first layer of tin, and that no oxide is deposited on the second layer of tin. Only the first three stages of the process are therefore carried out, those which are essential for obtaining the desired three-dimensional visual effect.
  • the heating of the tin layer is static and lasts 8 minutes in a lamp oven set at a temperature of 200 ° C. The result is visible in Figure 5.
  • EXAMPLE 6 A very thin sheet of 0.2 mm thick in mild steel 200 ⁇ 200 mm is coated with a layer of electrodeposited tin, so as to obtain a sheet of “tinplate” of the type usually used in the food sector. Then the second and third steps of the method according to the invention are carried out, under conditions identical to those of Example 2. The optional fourth step of the treatment according to the invention is not executed. The result is visible in Figure 6.
  • the sheet is coated with an aluminum layer of 0.6 ⁇ m by magnetron sputtering in an argon atmosphere under a pressure of 10 "3 mbar (0.1 Pa).
  • target is 1.8A and target voltage 355V
  • the deposition rate of aluminum is
  • the sheet is heat treated with an argon plasma under a pressure of 10 "3 mbar (0.1 Pa).
  • the energy imparted to the argon ions is 280 eV and the dose ion is 18.4.10 22 Ar + ions / m2.
  • the plate is placed as the cathode.
  • the surface of the coated aluminum is heated to a temperature of 615 ° C at the end of treatment.
  • a coating of tin is deposited by magnetron sputtering, under the same experimental conditions as those described in the third step of Example 1.
  • a coating is obtained under these conditions of development. identical to that of the example in FIG. 1.
  • This mild steel sheet is coated with tin under the same conditions as for Example 3 for the first two stages.
  • an aluminum coating is deposited by magnetron sputtering, under the same experimental conditions as those described in the first step of Example 7 except that an aluminum deposit of thickness 0 is produced. , 4 ⁇ m. Under these production conditions, a coating is obtained whose external appearance is identical to that of the example in FIG. 3.
  • the three-dimensional visual effect is obtained only on one or portions of the surface of the metallic material, it is possible to protect the material by one or more masks masking the areas not to be coated during the various treatments undergone.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Physical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention relates to a method for coating the surface of a metallic material having a crystallographic structure. The inventive method consists in producing a first coating of said material with a metal layer or a metal alloy layer having a melting point of Tf and a thickness equal to or less than 2.5νm, heating the first coating by a flash heating in such a way that it is heated to a temperature ranging from 0.8 Tf to Tf, producing a second metal or metal alloy coating with a thickness equal to or less than 1νm. The device for carrying out said method and the thus coated metallic material are also disclosed.

Description

Procédé de revêtement de la surface d'un matériau métallique, dispositif pour sa mise en oeuyre et produit ainsi obtenu.Method for coating the surface of a metallic material, device for using it and product thus obtained.
L'invention concerne le revêtement des surfaces métalliques. Plus précisément, elle concerne des traitements de revêtement de la surface d'un matériau métallique destinés à lui conférer un effet visuel tridimensionnel. Un tel effet visuel peut être obtenu avec des hologrammes, qui sont obtenus par l'enregistrement et la reproduction d'une image à l'aide de deux faisceaux laser sur un support photosensible capable d'enregistrer des interférences lumineuses de bon contraste. De tels supports sont, par exemple, des films thermoplastiques, des photopolymères, des films photosensibles... Jusqu'à présent, pour obtenir un effet visuel tridimensionnel sur une surface métallique, on ne connaît pas d'autre moyen que d'appliquer par collage ou colaminage sur ladite surface un support photosensible du type que l'on vient de décrire. La décoration d'emballages métalliques en acier ou aluminium est un usage privilégié de cette technique, qui a l'inconvénient, pour l'entreprise métallurgique, de nécessiter l'intervention d'un fournisseur extérieur qui lui livre le support photosensible. De plus, le support risque de se désolidariser de l'emballage ou d'être détérioré au cours des traitements et manipulations subis par ledit emballage postérieurement au collage ou au colaminage.The invention relates to the coating of metal surfaces. More specifically, it relates to treatments for coating the surface of a metallic material intended to give it a three-dimensional visual effect. Such a visual effect can be obtained with holograms, which are obtained by recording and reproducing an image using two laser beams on a photosensitive support capable of recording light interference of good contrast. Such supports are, for example, thermoplastic films, photopolymers, photosensitive films ... Up to now, to obtain a three-dimensional visual effect on a metal surface, no other means is known than to apply by bonding or co-laminating on said surface a photosensitive support of the type just described. The decoration of metallic packaging in steel or aluminum is a privileged use of this technique, which has the disadvantage, for the metallurgical enterprise, of requiring the intervention of an external supplier who delivers the photosensitive support to it. In addition, the support is liable to become detached from the packaging or to be damaged during the treatments and manipulations undergone by said packaging after bonding or co-laminating.
Le but de l'invention est de proposer un procédé permettant d'obtenir des effets visuels tridimensionnels sur la surface d'un matériau métallique sans avoir recours à l'application sur cette surface d'un support photosensible.The object of the invention is to propose a method making it possible to obtain three-dimensional visual effects on the surface of a metallic material without having recourse to the application to this surface of a photosensitive support.
A cet effet, l'invention a pour objet un procédé de revêtement de la surface d'un matériau métallique présentant une structure cristallographique, selon lequel on réalise un premier revêtement dudit matériau par une couche d'un métal ou d'un alliage métallique à point de fusion égal à Tf, d'épaisseur inférieure ou égale à 2,5μm, caractérisé en ce que :To this end, the subject of the invention is a method of coating the surface of a metallic material having a crystallographic structure, according to which a first coating of said material is carried out with a layer of a metal or of a metallic alloy with melting point equal to T f , of thickness less than or equal to 2.5 μm, characterized in that:
- on réalise un traitement thermique sur ledit premier revêtement par un moyen de chauffage rapide de manière à porter la surface dudit premier revêtement à une température comprise entre 0,8Tf et Tf; - et on réalise le dépôt d'un deuxième revêtement à partir d'un métal ou d'un alliage métallique, d'épaisseur inférieure ou égale à 1 μm.- A heat treatment is carried out on said first coating by a rapid heating means so as to bring the surface of said first coating to a temperature between 0.8T f and T f ; - And a second coating is deposited from a metal or a metal alloy, of thickness less than or equal to 1 μm.
Selon une variante du procédé, lesdits premier et deuxième revêtements ont des points de fusions inférieurs ou égaux à 700°C. Lesdits premier et deuxième revêtements peuvent être constitués par le même matériau.According to a variant of the method, said first and second coatings have melting points less than or equal to 700 ° C. Said first and second coatings can be made of the same material.
Selon une variante du procédé, on réalise ensuite le dépôt sur ledit deuxième revêtement d'une pellicule minérale transparente.According to a variant of the process, the deposition on said second coating is then carried out of a transparent mineral film.
Ledit matériau métallique à revêtir peut, de préférence, être un acier au carbone, un acier inoxydable, ou de l'aluminium ou un de ses alliages.Said metallic material to be coated may preferably be carbon steel, stainless steel, or aluminum or one of its alloys.
Ledit premier revêtement peut être, de préférence, réalisé par électrodéposition ou par un procédé de dépôt sous vide. Ledit moyen de chauffage rapide peut être, de préférence, un dispositif de chauffage par infra-rouges, un dispositif de chauffage par induction, un dispositif d'effluvage sous plasma avec un gaz non réactif ou un dispositif de bombardement ionique avec un gaz non réactif.Said first coating can preferably be produced by electrodeposition or by a vacuum deposition process. Said rapid heating means may preferably be an infrared heating device, an induction heating device, a plasma effluvium device with a non-reactive gas or an ion bombardment with a non-reactive gas .
Ledit deuxième revêtement peut être, de préférence, réalisé par électrodéposition ou par un procédé de dépôt sous vide.Said second coating can preferably be produced by electrodeposition or by a vacuum deposition process.
On peut déposer ladite pellicule minérale transparente par un procédé de dépôt par plasma réactif.Said transparent mineral film can be deposited by a reactive plasma deposition process.
Lesdits premier et deuxième revêtements peuvent être chacun constitués par de l'étain et/ou de l'aluminium. Ladite pellicule minérale peut être constituée par un oxyde métallique ou un mélange d'oxydes métalliques, de préférence choisis parmi les oxydes d'acier inoxydable austénitique, de chrome, de titane, de silicium, de zinc, d'étain.Said first and second coatings can each consist of tin and / or aluminum. Said mineral film can consist of a metal oxide or a mixture of metal oxides, preferably chosen from oxides of austenitic stainless steel, chromium, titanium, silicon, zinc, tin.
Le matériau métallique peut être sous forme d'une bande en défilement, et les différentes étapes du procédé peuvent être réalisées en continu au moyen d'installations disposées successivement sur le trajet de la bande en défilement.The metallic material can be in the form of a moving strip, and the various stages of the process can be carried out continuously by means of installations arranged successively on the path of the moving strip.
L'invention a également pour objet un dispositif pour le revêtement d'un matériau métallique sous forme de bande, caractérisé en ce qu'il comporte des moyens pour faire défiler ladite bande et, disposés successivement sur le trajet de ladite bande :The invention also relates to a device for coating a metallic material in the form of a strip, characterized in that it comprises means for scrolling said strip and, successively arranged on the path of said strip:
- des premiers moyens pour revêtir ladite bande par une couche d'un métal ou d'un alliage métallique à point de fusion égal à Tf ;- first means for coating said strip with a layer of a metal or a metal alloy with a melting point equal to T f ;
- des moyens de chauffage rapide de ladite bande pouvant porter la surface de ladite couche à une température comprise entre 0,8Tf et Tf ; et - des seconds moyens pour revêtir ladite bande par une couche, de métal ou d'alliage métallique.means for rapid heating of said strip which can bring the surface of said layer to a temperature between 0.8T f and T f ; and - second means for coating said strip with a layer of metal or metal alloy.
Le dispositif peut comporter, à la suite desdits seconds moyens pour revêtir ladite bande par une couche d'un métal ou d'un alliage métallique, des moyens pour revêtir ladite bande par une pellicule minérale transparente.The device may comprise, following said second means for coating said strip with a layer of a metal or a metal alloy, means for coating said strip with a transparent mineral film.
L'invention a également pour objet un matériau métallique, caractérisé en ce qu'il comporte sur l'une au moins de ses surfaces un revêtement métallique à effet visuel tridimensionnel, ledit revêtement étant formé directement sur ladite surface du matériau, et réalisé notamment par le procédé précédent. Comme on l'aura compris, l'invention consiste à obtenir l'effet visuel tridimensionnel recherché par une série de traitements de surface du matériau métallique lui-même. On obtient ainsi un revêtement multicouches qui ne peut être détaché du matériau métallique et est réalisable par l'entreprise métallurgique qui a fabriqué le matériau de base. Ce revêtement, outre ses qualités esthétiques, présente de nombreux avantages d'ordre technique, et permet au fabricant du matériau métallique de conserver l'entière maîtrise du processus de décoration.The invention also relates to a metallic material, characterized in that it comprises on at least one of its surfaces a metallic coating with a three-dimensional visual effect, said coating being formed directly on said surface of the material, and produced in particular by the previous process. As will be understood, the invention consists in obtaining the three-dimensional visual effect sought by a series of surface treatments of the metallic material itself. A multilayer coating is thus obtained which cannot be detached from the metallic material and can be produced by the metallurgical company which manufactured the basic material. This coating, in addition to its aesthetic qualities, has many technical advantages, and allows the manufacturer of the metallic material to retain complete control of the decoration process.
L'invention sera mieux comprise à la lecture de la description qui suit donnée en référence aux figures 1 à 6 annexées qui montrent les aspects de différents revêtements obtenus par diverses variantes du procédé selon l'invention.The invention will be better understood on reading the description which follows given with reference to appended FIGS. 1 to 6 which show the aspects of different coatings obtained by various variants of the method according to the invention.
Le matériau de départ est un matériau métallique, tel qu'un acier au carbone, un acier inoxydable, de l'aluminium ou un de ses alliages, etc. Il se présente par exemple sous forme d'une plaque ou d'une bande bobinée. Dans ce dernier cas, il est possible de réaliser le traitement qui va être décrit en débobinant la bande et en la faisant défiler en continu dans une installation où les appareillages permettant de réaliser les différentes étapes du traitement sont disposés à la suite les uns des autres sur le trajet de la bande. Pour que l'effet esthétique recherché soit obtenu, il est nécessaire que le matériau métallique utilisé comme substrat présente une structure cristallographique.The starting material is a metallic material, such as carbon steel, stainless steel, aluminum or an alloy thereof, etc. It is for example in the form of a plate or a wound strip. In the latter case, it is possible to carry out the treatment which will be described by unwinding the strip and scrolling it continuously in an installation where the apparatuses making it possible to carry out the different stages of the treatment are arranged one after the other. on the path of the strip. In order for the desired aesthetic effect to be obtained, the metallic material used as a substrate must have a crystallographic structure.
Avant de procéder au dépôt, on réalisera, de façon connue en soi, un avivage de la surface du matériau afin d'en éliminer toute contamination superficielle.Before proceeding with the deposition, in a manner known per se, a brightening of the surface of the material will be carried out in order to eliminate any surface contamination.
La première étape du procédé est le dépôt d'un premier revêtement, constitué par un élément métallique (étain ou aluminium, par exemple) ou un alliage métallique, de préférence à bas point de fusion Tf, de l'ordre de 700°C ou inférieur. Ce revêtement doit avoir une épaisseur inférieure ou égale à 2,5μm. Avantageusement, il est réalisé par un procédé d'électrodéposition, ou par un procédé de dépôt sous vide. Parmi les procédés de dépôt sous vide utilisables, on peut citer les procédés classiquement connus d'évaporation sous vide, de pulvérisation magnétron, de placage ionique, de placage ionique auto-induit (self- induced ion plating).The first process step is the deposition of a first coating, comprising a metallic member (aluminum or tin, for example) or a metal alloy, preferably low-melting point T f of the order of 700 ° C or lower. This coating must have a thickness less than or equal to 2.5 μm. Advantageously, it is produced by an electrodeposition process, or by a vacuum deposition process. Among the vacuum deposition methods which can be used, mention may be made of the conventionally known methods of vacuum evaporation, magnetron sputtering, ion plating, self-induced ion plating.
La deuxième étape du procédé est un traitement thermique effectué sur le premier revêtement, par un moyen de chauffage rapide, tel que des lampes à infra-rouge, un inducteur, un effluvage sous plasma, ou un bombardement ionique avec un gaz non réactif tel qu'un gaz rare. Ce traitement thermique doit porter la surface du premier revêtement à une température comprise entre 0,8 Tf et Tf. Pour qu'il s'effectue avec une cinétique compatible avec son exécution sur une bande défilant à une vitesse de l'ordre de 100m/mn, il est préférable que Tf soit inférieure ou égale à 700°C.The second stage of the process is a heat treatment carried out on the first coating, by a rapid heating means, such as infrared lamps, an inductor, a plasma effluvium, or an ion bombardment with a non-reactive gas such as 'a rare gas. This heat treatment must bring the surface of the first coating to a temperature between 0.8 T f and T f . For it to be carried out with kinetics compatible with its execution on a strip moving at a speed of the order of 100 m / min, it is preferable that T f be less than or equal to 700 ° C.
La troisième étape du procédé est le dépôt d'un deuxième revêtement, à partir d'un élément métallique ou d'un alliage identique ou non au matériau du premier revêtement. Ce revêtement doit avoir une épaisseur ne dépassant pas 1 μm. Il est réalisable par les mêmes méthodes que le premier revêtement.The third step of the process is the deposition of a second coating, from a metallic element or an alloy identical or not to the material of the first coating. This coating must have a thickness not exceeding 1 μm. It can be produced by the same methods as the first coating.
Préférentiellement (mais pas obligatoirement), le procédé peut comporter une quatrième étape consistant à déposer sur le deuxième revêtement métallique une pellicule minérale transparente. Des matériaux tels que des oxydes d'acier inoxydable austénitique, de chrome, de titane, de silicium, de zinc, d'étain (liste non limitative) et leurs mélanges sont particulièrement indiqués. Ce dépôt minéral transparent peut être réalisé par tout moyen connu à cet effet, les procédés utilisant un dépôt par plasma réactif étant particulièrement indiqués. Si cette pellicule a une épaisseur inférieure ou égale à 1 μm, on peut obtenir un revêtement coloré par effet interférentiel du film minéral. Des couleurs verte, jaune, bleue, violette et rouge sont accessibles de cette manière, en fonction de l'indice de réfraction du matériau déposé. De manière générale, cette pellicule transparente donne une apparence de profondeur supplémentaire aux motifs d'apparence tridimensionnelle obtenus à la suite des trois premières étapes du procédé.Preferably (but not necessarily), the method may include a fourth step consisting in depositing on the second metallic coating a transparent mineral film. Materials such as oxides of austenitic stainless steel, chromium, titanium, silicon, zinc, tin (non-limiting list) and their mixtures are particularly indicated. This transparent mineral deposition can be carried out by any means known for this purpose, the methods using a reactive plasma deposition being particularly indicated. If this film has a thickness less than or equal to 1 μm, a colored coating can be obtained by interference effect of the mineral film. Green, yellow, blue, purple and red colors are accessible in this way, depending on the refractive index of the deposited material. In general, this transparent film gives an appearance of additional depth to the three-dimensional appearance patterns obtained following the first three steps of the process.
L'apparition de motifs à la surface du substrat nécessite, comme on l'a dit, que ce dernier possède une structure cristallographique. En effet, la germination des motifs de solidification des dépôts métalliques se produit sur la base de sites préférentiels à la surface du substrat, qui n'existent que si le substrat possède une structure cristallographique.The appearance of patterns on the surface of the substrate requires, as has been said, that the latter has a crystallographic structure. Indeed, the germination of the solidification patterns of the metal deposits occurs on the basis of preferential sites on the surface of the substrate, which exist only if the substrate has a crystallographic structure.
La taille des motifs obtenus dépend de la quantité d'énergie mise en oeuvre lors de la deuxième étape du procédé et de l'épaisseur du revêtement : les motifs seront d'autant plus grands que cette quantité d'énergie et/ou cette épaisseur seront importantes. L'utilisation, comme matériau de revêtement lors de la première étape du procédé, d'un métal ou alliage à bas point de fusion (700°C ou moins) permet de réaliser la transformation métallurgique du revêtement lors de la deuxième étape dans un temps très bref. Les procédés de chauffage qui ont été cités permettent d'apporter l'énergie nécessaire en un minimum de temps.The size of the patterns obtained depends on the amount of energy used during the second step of the process and on the thickness of the coating: the patterns will be all the greater as this amount of energy and / or this thickness will be important. The use, as coating material during the first step of the process, of a metal or alloy with a low melting point (700 ° C. or less) makes it possible to carry out the metallurgical transformation of the coating during the second step in a time very brief. The heating methods which have been mentioned make it possible to provide the necessary energy in a minimum of time.
Par rapport à l'obtention d'effets visuels tridimensionnels par des supports photosensibles appliqués sur le produit métallique, le procédé selon l'invention présente plusieurs avantages. Comme on l'a dit, il permet au fabricant de produits métalliques de conserver l'entière maîtrise du procédé. Le revêtement générant l'effet visuel tridimensionnel étant ici une partie intégrante du support, il ne risque pas de s'en détacher au cours des traitements et des manipulations ultérieurs. De plus, tout particulièrement si le procédé est utilisé dans sa version complète à quatre étapes, le revêtement ainsi obtenu améliore la résistance du substrat à la corrosion cosmétique. Le revêtement est également plus résistant aux ultra-violets et à la température. Il est moins sensible aux traces de doigt. Il est d'une grande dureté superficielle, ce qui le rend moins sensible aux rayures. Il est facile à nettoyer et résiste bien aux produits d'entretien et autres sollicitations mécaniques. Enfin, il est possible, si le métal de revêtement utilisé s'y prête (par exemple l'étain), de rendre le revêtement compatible avec un usage alimentaire.Compared to obtaining three-dimensional visual effects by photosensitive supports applied to the metal product, the method according to the invention has several advantages. As we said, it allows the manufacturer of metal products to retain full control of the process. The coating generating the three-dimensional visual effect here being an integral part of the support, there is no risk of it coming off during subsequent treatments and manipulations. In addition, especially if the process is used in its complete four-stage version, the coating thus obtained improves the resistance of the substrate to cosmetic corrosion. The coating is also more resistant to ultraviolet and temperature. It is less sensitive to fingerprints. It has great surface hardness, which makes it less susceptible to scratches. It is easy to clean and is resistant to cleaning products and other mechanical stresses. Finally, it is possible, if the coating metal used is suitable (for example tin), to make the coating compatible with food use.
Différents exemples de mise en oeuvre du procédé selon l'invention vont à présent être décrits. Ils ont été exécutés sur des tôles d'acier doux de 200 x 200mm et 0,7mm d'épaisseur. Ces tôles ont été préalablement dégraissées classiquement par voie humide (solvant agité par des ultras-sons). Puis elles ont été soumises à un décapage ionique à partir d'un plasma d'argon dans un réacteur sous vide qui a ensuite été utilisé lors des différentes étapes de réalisation du procédé selon l'invention.Different examples of implementation of the method according to the invention will now be described. They were executed on mild steel sheets 200 x 200mm and 0.7mm thick. These sheets have previously been degreased conventionally by the wet method (solvent stirred by ultrasound). Then they were subjected to an ion pickling from an argon plasma in a vacuum reactor which was then used during the various stages of carrying out the process according to the invention.
Exemple 1Example 1
Dans la première étape du procédé selon l'invention, la tôle est revêtue par une couche d'étain de 0,8μm par pulvérisation magnétron en atmosphère d'argon sous une pression de 10"3 mbar (0,1 Pa). Le courant cible est de 0,9A et la tension cible de 450V. La vitesse de dépôt de l'étain est de 0,25μm/min.In the first step of the process according to the invention, the sheet is coated with a 0.8 μm layer of tin by magnetron sputtering in an argon atmosphere under a pressure of 10 "3 mbar (0.1 Pa). target is 0.9A and the target voltage is 450 V. The tin deposition rate is 0.25μm / min.
Dans la deuxième étape du procédé selon l'invention, la tôle est traitée thermiquement par un plasma d'argon sous une pression de 10"3 mbar (0,1 Pa). L'énergie conférée aux ions d'argon est de 400 eV et la dose d'ions reçue par la tôle est de 4,7.1022 ions ArVm2. La tôle est placée en cathode. La surface de l'étain est portée à une température de l'ordre de 210°C.In the second step of the process according to the invention, the sheet is heat treated with an argon plasma under a pressure of 10 "3 mbar (0.1 Pa). The energy given to the argon ions is 400 eV and the dose of ions received by the sheet is 4.7.10 22 ArVm 2 ions. The sheet is placed as a cathode. The surface of the tin is brought to a temperature of the order of 210 ° C.
Dans la troisième étape, on dépose un revêtement d'étain de 0,4 μm par pulvérisation magnétron, dans les mêmes conditions expérimentales que pour le premier revêtement.In the third step, a 0.4 μm tin coating is deposited by magnetron sputtering, under the same experimental conditions as for the first coating.
Dans la quatrième étape, on procède au dépôt par plasma CVD d'une pellicule transparente de silice, d'une épaisseur de 0,1 μm. Le dépôt est réalisé dans une atmosphère composée d'hexaméthyldisiloxane (HMDSO) et d'oxygène, sous une pression de 10"3 mbar (0,1 Pa), avec un rapport des pressions partielles de HMDSO et d'O2 de 1/10. On utilise un courant de fréquence 50 kHz à une puissance de 100W. La vitesse de dépôt est de 1 ,0μm/min.In the fourth step, CVD plasma is deposited with a transparent silica film, with a thickness of 0.1 μm. The deposition is carried out in an atmosphere composed of hexamethyldisiloxane (HMDSO) and oxygen, under a pressure of 10 "3 mbar (0.1 Pa), with a ratio of the partial pressures of HMDSO and O 2 of 1 / 10. A frequency current of 50 kHz is used at a power of 100 W. The deposition rate is 1.0 μm / min.
On obtient par ce procédé un revêtement dont l'aspect extérieur est représenté sur la figure 1 , ayant des propriétés anti-corrosion et anti-trace de doigt, facile à nettoyer, et présentant une grande dureté superficielle. Il est apte à résister à des sollicitations mécaniques, chimiques et thermiques élevées.This coating gives a coating whose external appearance is shown in FIG. 1, having anti-corrosion and anti-fingerprint properties, easy to clean, and having a high surface hardness. It is able to withstand high mechanical, chemical and thermal stresses.
Exemple 2Example 2
On réalise un revêtement de ladite tôle d'acier dans des conditions identiques à celles de l'exemple 1 pour les trois premières étapes. La quatrième étape consiste en la réalisation d'une pellicule d'oxyde de titane colorée par pulvérisation magnétron réactive d'une cible de titane. Son épaisseur est de 0,05 μm. Les conditions de sa réalisation sont une atmosphère O2/Ar avec 0,4, une pression totale de 5.10"3 mbar (10,5Pa) et une puissance de 1 ,7kW. On obtient ainsi un revêtement représenté sur la figure 2, présentant des propriétés analogues à celui de l'exemple 1 , avec en plus un aspect coloré en bleu du fait de l'indice de réfraction de l'oxyde de titane (2,5) et les propriétés particulières à l'oxyde de titane, à savoir une grande inertie chimique, une bonne tenue à haute température, une bonne résistance aux attaques chimiques, et une action autonettoyante due à son effet catalytique de dégradation des matières contenant du carbone et de l'oxygène en présence de lumière ultra-violette.A coating of said steel sheet is carried out under conditions identical to those of Example 1 for the first three stages. The fourth step consists in producing a titanium oxide film colored by reactive magnetron sputtering of a titanium target. Its thickness is 0.05 μm. The conditions for its realization are an O 2 / Ar atmosphere with 0.4, a total pressure of 5.10 "3 mbar (10.5 Pa) and a power of 1.7 kW. This gives a coating represented in FIG. 2, having properties similar to that of Example 1, with in plus a blue colored appearance due to the refractive index of titanium oxide (2.5) and the properties specific to titanium oxide, namely great chemical inertness, good resistance to high temperature, good resistance to chemical attack, and a self-cleaning action due to its catalytic effect of degradation of materials containing carbon and oxygen in the presence of ultraviolet light.
Exemple 3Example 3
On réalise un revêtement de ladite tôle d'acier doux dans les mêmes conditions que pour l'exemple 2, à ceci près que l'on augmente l'épaisseur du premier dépôt d'étain jusqu'à 1 ,2 μm, ainsi que la dose d'ions reçue par la première couche d'étain lors de la deuxième étape du procédé. Cette dose atteint ici 9,4.1022 ions Ar"7m2. La surface de l'étain est portée à une température de l'ordre de 235°C. Le résultat est visible sur la figure 3.This mild steel sheet is coated under the same conditions as for Example 2, except that the thickness of the first deposit of tin is increased to 1.2 μm, as well as the dose of ions received by the first layer of tin during the second step of the process. This dose reaches here 9.4.10 22 Ar " 7m 2 ions. The surface of the tin is brought to a temperature of the order of 235 ° C. The result is visible in FIG. 3.
Exemple 4_ On réalise un revêtement de ladite tôle d'acier doux dans les mêmes conditions que pour l'exemple 2, à ceci près que, comme pour l'exemple 3, on augmente la dose d'ions reçue par la première couche à 9,4.1022 ions Ar+/m2, et qu'on augmente l'épaisseur de la pellicule d'oxyde de titane à 0,08μm. Le résultat est visible sur la figure 4. On remarque que l'augmentation de l'énergie mise en œuvre lors de la deuxième étape du traitement conduit à une augmentation substantielle de la taille des motifs.EXAMPLE 4 A coating of said mild steel sheet is carried out under the same conditions as for Example 2, except that, as in Example 3, the dose of ions received by the first layer is increased to 9 , 4.10 22 Ar + ions / m 2 , and increasing the thickness of the titanium oxide film to 0.08 μm. The result is visible in FIG. 4. It is noted that the increase in energy used during the second stage of the treatment leads to a substantial increase in the size of the patterns.
Exemple 5 On effectue le revêtement de ladite tôle dans des conditions identiques à celles de l'exemple 1 , à ceci près qu'on utilise, pour la deuxième étape, deux lampes à infra-rouges pour réaliser le chauffage du substrat et de sa première couche d'étain, et qu'on ne dépose pas d'oxyde sur la deuxième couche d'étain. On ne réalise donc que les trois premières étapes du procédé, celles qui sont indispensables pour obtenir l'effet visuel tridimensionnel recherché. Le chauffage de la couche d'étain est statique et dure 8 minutes dans un four à lampes réglé à une température de 200°C. Le résultat est visible sur la figure 5.EXAMPLE 5 The said sheet is coated under conditions identical to those of Example 1, except that, for the second step, two infrared lamps are used to heat the substrate and its first layer of tin, and that no oxide is deposited on the second layer of tin. Only the first three stages of the process are therefore carried out, those which are essential for obtaining the desired three-dimensional visual effect. The heating of the tin layer is static and lasts 8 minutes in a lamp oven set at a temperature of 200 ° C. The result is visible in Figure 5.
Exemple 6 On effectue le revêtement d'une tôle très mince de 0,2mm d'épaisseur en acier doux de 200 x 200mm par une couche d'étain électrodéposée, de manière à obtenir une tôle en « fer blanc » du type habituellement utilisé dans le domaine alimentaire. Puis les deuxième et troisième étapes du procédé selon l'invention sont exécutées, dans des conditions identiques à celles de l'exemple 2. On n'exécute pas la quatrième étape optionnelle du traitement selon l'invention. Le résultat est visible sur la figure 6.EXAMPLE 6 A very thin sheet of 0.2 mm thick in mild steel 200 × 200 mm is coated with a layer of electrodeposited tin, so as to obtain a sheet of “tinplate” of the type usually used in the food sector. Then the second and third steps of the method according to the invention are carried out, under conditions identical to those of Example 2. The optional fourth step of the treatment according to the invention is not executed. The result is visible in Figure 6.
Exemple 7Example 7
Dans une première étape du procédé selon l'invention, la tôle est revêtue par une couche d'aluminium de 0,6μm par pulvérisation magnétron en atmosphère d'argon sous une pression de 10"3 mbar (0,1 Pa). Le courant cible est de 1 ,8A et la tension cible de 355V. La vitesse de dépôt de l'aluminium est deIn a first step of the process according to the invention, the sheet is coated with an aluminum layer of 0.6 μm by magnetron sputtering in an argon atmosphere under a pressure of 10 "3 mbar (0.1 Pa). target is 1.8A and target voltage 355V The deposition rate of aluminum is
0,33μm/min. Dans la deuxième étape du procédé selon l'invention, la tôle est traitée thermiquement par un plasma d'argon sous une pression de 10"3 mbar (0,1 Pa). L'énergie conférée aux ions argon est de 280eV et la dose d'ions est de 18.4.1022 ions Ar+/m2. La tôle est placée en cathode. La surface de la tôle revêtue d'aluminium est portée à une température de 615°C à la fin du traitement.0,33μm / min. In the second step of the process according to the invention, the sheet is heat treated with an argon plasma under a pressure of 10 "3 mbar (0.1 Pa). The energy imparted to the argon ions is 280 eV and the dose ion is 18.4.10 22 Ar + ions / m2. the plate is placed as the cathode. the surface of the coated aluminum is heated to a temperature of 615 ° C at the end of treatment.
Dans une troisième étape, on dépose un revêtement d'étain par pulvérisation magnétron, dans les mêmes conditions expérimentales que celles décrites dans la troisième étape de l'exemple 1. On obtient dans ces conditions d'élaboration un revêtement dont l'aspect extérieur est identique à celui de l'exemple de la figure 1.In a third step, a coating of tin is deposited by magnetron sputtering, under the same experimental conditions as those described in the third step of Example 1. A coating is obtained under these conditions of development. identical to that of the example in FIG. 1.
Exemple 8Example 8
On réalise un revêtement de ladite tôle d'acier doux par de l'étain dans les mêmes conditions que pour l'exemple 3 pour les deux premières étapes. Dans une troisième étape, on dépose un revêtement d'aluminium par pulvérisation magnétron, dans les mêmes conditions expérimentales que celles décrites dans la première étape de l'exemple 7 à ceci près que l'on réalise un dépôt d'aluminium d'épaisseur 0,4μm. On obtient dans ces conditions d'élaboration un revêtement dont l'aspect extérieur est identique à celui de l'exemple de la figure 3.This mild steel sheet is coated with tin under the same conditions as for Example 3 for the first two stages. In a third step, an aluminum coating is deposited by magnetron sputtering, under the same experimental conditions as those described in the first step of Example 7 except that an aluminum deposit of thickness 0 is produced. , 4μm. Under these production conditions, a coating is obtained whose external appearance is identical to that of the example in FIG. 3.
Les exemples de matériaux formant le substrat et les différentes couches qui le revêtent, ainsi que les conditions de leur formation ont été données à titre non limitatif. L'homme du métier pourra imaginer des variantes en fonction des propriétés recherchées pour le produit final.The examples of materials forming the substrate and the different layers which coat it, as well as the conditions for their formation have been given without limitation. Those skilled in the art can imagine variants depending on the properties sought for the final product.
Si on désire que l'effet visuel tridimensionnel ne soit obtenu que sur une ou des portions de la surface du matériau métallique, il est possible de protéger le matériau par un ou des caches masquant les zones à ne pas revêtir lors des divers traitements subis. If it is desired that the three-dimensional visual effect is obtained only on one or portions of the surface of the metallic material, it is possible to protect the material by one or more masks masking the areas not to be coated during the various treatments undergone.

Claims

REVENDICATIONS
1. Procédé de revêtement de la surface d'un matériau métallique présentant une structure cristallographique, selon lequel on réalise un premier revêtement dudit matériau par une couche d'un métal ou d'un alliage métallique à point de fusion égal à Tf , d'épaisseur inférieure ou égale à 2,5μm, caractérisé en ce que :1. A method of coating the surface of a metallic material having a crystallographic structure, according to which a first coating of said material is carried out with a layer of a metal or of a metallic alloy with a melting point equal to T f , d '' thickness less than or equal to 2.5μm, characterized in that:
- on réalise un traitement thermique sur ledit premier revêtement par un moyen de chauffage rapide de manière à porter la surface dudit premier revêtement à une température comprise entre 0,8Tf et Tf; - et on réalise le dépôt d'un deuxième revêtement à partir d'un métal ou d'un alliage métallique, d'épaisseur inférieure ou égale à 1 μm.- A heat treatment is carried out on said first coating by rapid heating means so as to bring the surface of said first coating to a temperature between 0.8T f and T f ; - And a second coating is made from a metal or a metal alloy, of thickness less than or equal to 1 μm.
2. Procédé selon la revendication 1 , caractérisé en ce que lesdits premier et deuxième revêtements ont des points de fusions inférieurs ou égaux à 700°C. 2. Method according to claim 1, characterized in that said first and second coatings have melting points less than or equal to 700 ° C.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que lesdits premier et deuxième revêtements sont constitués par le même matériau.3. Method according to claim 1 or 2, characterized in that said first and second coatings are made of the same material.
4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce qu'on réalise ensuite le dépôt sur ledit deuxième revêtement d'une pellicule minérale transparente. 4. Method according to one of claims 1 to 3, characterized in that the deposition is then carried out on said second coating of a transparent mineral film.
5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que ledit matériau métallique à revêtir est un acier au carbone.5. Method according to one of claims 1 to 4, characterized in that said metallic material to be coated is carbon steel.
6. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que ledit matériau métallique à revêtir est un acier inoxydable.6. Method according to one of claims 1 to 4, characterized in that said metallic material to be coated is stainless steel.
7. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que ledit matériau métallique à revêtir est de l'aluminium ou un de ses alliages.7. Method according to one of claims 1 to 4, characterized in that said metallic material to be coated is aluminum or one of its alloys.
8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que ledit premier revêtement est réalisé par électrodéposition.8. Method according to one of claims 1 to 7, characterized in that said first coating is produced by electrodeposition.
9. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que ledit premier revêtement est réalisé par un procédé de dépôt sous vide. 9. Method according to one of claims 1 to 7, characterized in that said first coating is produced by a vacuum deposition process.
10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que ledit moyen de chauffage rapide est un dispositif de chauffage par infrarouges.10. Method according to one of claims 1 to 9, characterized in that said rapid heating means is an infrared heating device.
11. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que ledit moyen de chauffage rapide est un dispositif de chauffage par induction. 11. Method according to one of claims 1 to 9, characterized in that said rapid heating means is an induction heating device.
12. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que ledit moyen de chauffage rapide est un dispositif d'effluvage sous plasma avec un gaz non réactif.12. Method according to one of claims 1 to 9, characterized in that said rapid heating means is a device for effluvage under plasma with a non-reactive gas.
13. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que ledit moyen de chauffage rapide est un dispositif de bombardement ionique avec un gaz non réactif.13. Method according to one of claims 1 to 9, characterized in that said rapid heating means is an ion bombardment device with a non-reactive gas.
14. Procédé selon l'une des revendications 1 à 13, caractérisé en ce que ledit deuxième revêtement est réalisé par électrodéposition.14. Method according to one of claims 1 to 13, characterized in that said second coating is produced by electrodeposition.
15. Procédé selon l'une des revendications 1 à 13, caractérisé en ce que ledit deuxième revêtement est réalisé par un procédé de dépôt sous vide.15. Method according to one of claims 1 to 13, characterized in that said second coating is produced by a vacuum deposition process.
16. Procédé selon l'une des revendications 4 à 15, caractérisé en ce qu'on dépose ladite pellicule minérale transparente par un procédé de dépôt par plasma réactif.16. Method according to one of claims 4 to 15, characterized in that the said transparent mineral film is deposited by a reactive plasma deposition process.
17. Procédé selon l'une des revendications 1 à 16, caractérisé en ce que ledit premier et/ou ledit deuxième revêtement sont constitués par de l'étain.17. Method according to one of claims 1 to 16, characterized in that said first and / or said second coating consist of tin.
18. Procédé selon l'une des revendications 1 à 17, caractérisé en ce que ledit premier et/ou ledit deuxième revêtement sont constitués par de l'aluminium.18. Method according to one of claims 1 to 17, characterized in that said first and / or said second coating consist of aluminum.
19. Procédé selon l'une des revendications 1 à 18, caractérisé en ce que ladite pellicule minérale est constituée par un oxyde métallique ou un mélange d'oxydes métalliques.19. Method according to one of claims 1 to 18, characterized in that said mineral film consists of a metal oxide or a mixture of metal oxides.
20. Procédé selon la revendication 19, caractérisé en ce que le ou lesdits oxydes métalliques sont choisis parmi les oxydes d'acier inoxydable austénitique, de chrome, de titane, de silicium, de zinc, d'étain. 20. The method of claim 19, characterized in that the said metal oxide (s) are chosen from oxides of austenitic stainless steel, chromium, titanium, silicon, zinc, tin.
21. Procédé selon l'une des revendications 1 à 20, caractérisé en ce que le matériau métallique est sous forme d'une bande en défilement, et en ce que les différentes étapes du procédé sont réalisées en continu au moyen d'installations disposées successivement sur le trajet de la bande en défilement. 21. Method according to one of claims 1 to 20, characterized in that the metallic material is in the form of a moving strip, and in that the various stages of the method are carried out continuously by means of installations arranged successively on the path of the running tape.
22. Dispositif pour le revêtement d'un matériau métallique sous forme de bande, caractérisé en ce qu'il comporte des moyens pour faire défiler ladite bande et, disposés successivement sur le trajet de ladite bande :22. Device for coating a metallic material in the form of a strip, characterized in that it comprises means for scrolling said strip and, arranged successively on the path of said strip:
- des premiers moyens pour revêtir ladite bande par une couche d'un métal ou d'un alliage métallique à point de fusion égal à Tf ; - des moyens de chauffage rapide de ladite bande pouvant porter la surface de ladite couche à une température comprise entre 0,8Tf et Tf ; et- first means for coating said strip with a layer of a metal or a metal alloy with a melting point equal to T f ; means for rapid heating of said strip which can bring the surface of said layer to a temperature between 0.8T f and T f ; and
- des seconds moyens pour revêtir ladite bande par une couche de métal ou d'alliage métallique. - second means for coating said strip with a layer of metal or metal alloy.
23. Dispositif selon la revendication 22, caractérisé en ce qu'il comporte, à la suite desdits seconds moyens pour revêtir ladite bande par une couche d'un métal ou d'un alliage métallique, des moyens pour revêtir ladite bande par une pellicule minérale transparente.23. Device according to claim 22, characterized in that it comprises, following said second means for coating said strip with a layer of a metal or a metal alloy, means for coating said strip with a mineral film transparent.
24. Matériau métallique, caractérisé en ce qu'il comporte sur l'une au moins de ses surfaces un revêtement métallique à effet visuel tridimensionnel, ledit revêtement étant formé directement sur ladite surface du matériau.24. Metallic material, characterized in that it comprises, on at least one of its surfaces, a metallic coating with a three-dimensional visual effect, said coating being formed directly on said surface of the material.
25. Matériau métallique selon la revendication 24, caractérisé en ce qu'il est réalisé par le procédé selon l'une des revendications 1 à 21. 25. Metallic material according to claim 24, characterized in that it is produced by the method according to one of claims 1 to 21.
EP03758204A 2002-08-05 2003-08-04 Method for coating the surface of metallic material, device for carrying out said method Withdrawn EP1527208A2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0209952A FR2843130B1 (en) 2002-08-05 2002-08-05 METHOD FOR COATING THE SURFACE OF A METAL MATERIAL, DEVICE FOR IMPLEMENTING SAME AND PRODUCT THUS OBTAINED
FR0209952 2002-08-05
PCT/FR2003/002457 WO2004015169A2 (en) 2002-08-05 2003-08-04 Method for coating the surface of metallic material, device for carrying out said method

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US (1) US20060096674A1 (en)
EP (1) EP1527208A2 (en)
JP (1) JP2005534812A (en)
CN (1) CN1681966A (en)
AU (1) AU2003274221A1 (en)
BR (1) BR0313580A (en)
CA (1) CA2495457A1 (en)
FR (1) FR2843130B1 (en)
PL (1) PL373077A1 (en)
RU (1) RU2300579C2 (en)
WO (1) WO2004015169A2 (en)

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RU2300579C2 (en) 2007-06-10
US20060096674A1 (en) 2006-05-11
AU2003274221A1 (en) 2004-02-25
CN1681966A (en) 2005-10-12
FR2843130A1 (en) 2004-02-06
AU2003274221A8 (en) 2004-02-25
WO2004015169A2 (en) 2004-02-19
BR0313580A (en) 2005-07-12
RU2005106284A (en) 2005-07-27
CA2495457A1 (en) 2004-02-19
WO2004015169A3 (en) 2004-05-13
FR2843130B1 (en) 2004-10-29
JP2005534812A (en) 2005-11-17

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