EP0658637B1 - Process and apparatus for the dry treatment of metallic surfaces - Google Patents

Process and apparatus for the dry treatment of metallic surfaces Download PDF

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Publication number
EP0658637B1
EP0658637B1 EP19940402726 EP94402726A EP0658637B1 EP 0658637 B1 EP0658637 B1 EP 0658637B1 EP 19940402726 EP19940402726 EP 19940402726 EP 94402726 A EP94402726 A EP 94402726A EP 0658637 B1 EP0658637 B1 EP 0658637B1
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European Patent Office
Prior art keywords
gas
tunnel
process according
gaseous mixture
excited
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EP19940402726
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German (de)
French (fr)
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EP0658637A1 (en
Inventor
Thierry Sindzingre
Stéphane 14 Rés. du Parc du Château Rabia
Daniel Rés. du Val Fleuri Guerin
Christian Larquet
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents

Definitions

  • the present invention relates to the stages of preparation or treatment of metal surfaces involved in the production or production processes recovery of flat products (such as metal sheets) or hollow bodies (bottles, valves ).
  • these preparation stages perform cleaning, degreasing or activation of the surface, often before a subsequent process, which can be, for example, annealing, electroplating zinc, aluminum, tin or their alloys or the deposition of organic coatings such as varnishes or paints, or inorganic such as nitrides or films based on silicon.
  • Such a surface preparation step may also take place at the end of chain, for example just before coiling such metal sheets.
  • affected products are steel, stainless steel, copper or by aluminum example.
  • phase liquid we find first of all methods in phase liquid.
  • the generally preferred gaseous atmosphere for this method of pickling under electric discharge contains a high percentage of argon for its quality of highly plasmagenic gas and for the high mass of its ions which makes this gas suitable for spraying action, it is moreover enriched with oxygen or even hydrogen to take advantage of the chemical action of the discharge by eliminating the organic bodies present on the surface of the sheet by the formation of light compounds of the CO x or CH y type .
  • the method of treating surfaces by the dry route of at least one portion of metal surface is characterized in that the portion of metal surface is treated, at a pressure close to atmospheric pressure, by a treatment gas atmosphere comprising excited species or unstable and being substantially free of electrically charged species.
  • metal surface means any type of surface, whether it either for example steel, stainless steel, copper, or aluminum, whatever the dimension or thickness of the part comprising the surface portion (s) metal to be treated. Their final industrial application can be very varied, whether these metal surfaces are for example used in the field of household appliances, automotive, industrial gases or in the building industry or packaging.
  • surface treatment means any step preparation, cleaning, activation or degreasing of the surface portion metallic, this step being able to intervene in very different places of the chain of manufacture of products using such metal surfaces (whether flat as that for example sheets, or hollow such as for example bottles), this step can intervene at the end of the chain (before for example the rewinding of such metal sheets) or during production, before a subsequent process, which may for example be an annealing, an operation such as zinc plating, aluminum, tin or their alloys, or the deposition of organic coatings such as varnish or paint, or inorganic such as nitride or films based on silicon.
  • the application of the surface treatment method according to the invention will then have in particular to facilitate the application of the subsequent process, for example, facilitate the attachment of a paint coating.
  • the application of the surface treatment method according to the invention can then intervene alone or in addition to another surface preparation method, performed before or after the application of the process according to the invention.
  • pressure close to atmospheric pressure means a pressure which lies in the range [0.1 ⁇ 10 5 Pa, 3 ⁇ 10 5 Pa].
  • the treatment atmosphere according to the invention is distinguished from plasma atmospheres classics by the fact that it is substantially devoid of cash electrically charged, ie ions or electrons.
  • the treatment gas atmosphere is obtained from a gas mixture primary and an adjacent gas mixture, the primary gas mixture being obtained at the gas outlet of at least one apparatus for forming gaseous species excited or unstable in which an initial gas mixture has been transformed comprising an inert gas and / or a reducing gas and / or an oxidizing gas, the mixture adjacent having not passed through the device.
  • the apparatus according to the invention is constituted by any device allowing "to excite" an initial gas mixture, to obtain, at the gas outlet of the device, another gas mixture comprising unstable or excited gaseous species, the latter gas mixture being substantially free of electrically charged species, such an excitation being obtained by electric discharge, by example of the crown discharge type.
  • This configuration can be described as "post-discharge” since the primary component of the treatment atmosphere, which includes excited or unstable gaseous species, is obtained at the device outlet , which ensures the substantial absence of any species electrically. loaded into this primary component.
  • the adjacent component of the treatment atmosphere, which has not passed through the device, is a fortiori devoid of it.
  • this configuration makes it possible to clearly separate the place from the generation of the primary component of the atmosphere of the place of its use, which has a significant advantage in terms of pollution of the device (avoid that various clearances resulting from the surface treatment operation will not pollute inside the device, for example its electrodes).
  • the play, which is not treated within the device (for example within the discharge between the electrodes) benefits from much better flexibility on the "distance" aspect mentioned above.
  • the inert gas can for example consist of nitrogen, argon, helium or a mixture of such inert gases.
  • the reducing gas can for example consist of hydrogen, CH 4 , natural gas, propane or even ammonia or a mixture of such reducing gases.
  • the oxidizing gas can for example consist of oxygen, or CO 2 , or even N 2 O, H 2 O or a mixture of such oxidizing gases. The list of gases given in each category is of course only indicative, in no way limiting.
  • the initial gas mixture according to the invention is treated or transformed in at least one training device excited or unstable gaseous species, so as to obtain a gas outlet from said gas device, a so-called primary gas mixture comprising excited gas species or unstable.
  • the part comprising the portion (s) of surfaces to be treated may be brought into contact with the mixture primary gaseous obtained at the gas outlet of a single species-forming apparatus excited or unstable gases or of several devices placed in parallel on the width of the room or successively with the primary gas mixtures obtained at gas outlets from multiple excited gaseous species forming devices or unstable placed in series.
  • the method according to the invention is applied according to the needs expressed by the user both when treating only one side of the part to be treated and when it is necessary treat the part on both sides. In the latter case, the required devices next to each side of the room.
  • the adjacent mixture may consist of any gas or mixture of gases, for example an inert gas or mixture of inert gases making it possible to if necessary, maintain a protective atmosphere around the parts, or reducing gas or an oxidizing gas, or even a mixture of gases belonging to one of these three categories.
  • an inert gas or mixture of inert gases making it possible to if necessary, maintain a protective atmosphere around the parts, or reducing gas or an oxidizing gas, or even a mixture of gases belonging to one of these three categories.
  • the adjacent mixture contains silane SiH 4 .
  • Such an adjacent mixture containing silane is advantageously used for its reducing action with respect to certain metal oxides present on the surface of the part, but also, depending on the initial gas mixture used, as a "lookout” (or trap).
  • oxygen that is to say in its interaction with the residual oxygen of the atmosphere present above the room, with the aim of reducing to a minimum this level of residual oxygen.
  • the portion of metal surface to process is brought to a temperature not exceeding 600 ° C, typically between room temperature and 600 ° C.
  • the part comprising the portion to to be treated is brought opposite the gas outlet of said device, if necessary opposite gas outlets of several appliances placed in parallel across the width of the room and / or successively opposite the gas outlets of several devices placed in series, by a conveyor system crossing an interior space delimited by a tunnel or a casing assembly, isolated from the surrounding atmosphere, said tunnel or assembly being tightly connected to said device or including said device.
  • the conveyor according to the invention may, depending on the industry considered, for example consist of a carpet or in the case of metal sheets by rollers.
  • the apparatus in which is transformed said initial gas mixture is the seat of an electrical discharge created between a first electrode and a second electrode, a layer of material being placed on the surface of at least one of the electrodes, facing the other electrode, the initial gas mixture crossing the discharge transversely to the electrodes.
  • the energy used in the device, reduced to the dielectric surface unit will then advantageously be greater than 1W / cm 2 , preferably greater than 10W / cm 2.
  • steps a) and b) above may relate to the same device.
  • the invention also relates to the use of a dry surface treatment device at least a portion of metal surface, device comprising a tunnel or a casing assembly defining an interior space traversed by means of conveying the pieces comprising the portion (s) of surfaces to be treated, airtight vis-à-vis the atmosphere surrounding area, sealingly connected or including one or more formation of excited or unstable gas species mounted in series and / or parallel comprising at least one tubular gas passage having an axis, formed between a external electrode and an internal electrode, at least one of the electrodes comprising, facing each other, a dielectric coating, the electrodes being connected to a high voltage and high frequency source, the outer electrode surrounding the dielectric and comprising a so-called initial gas inlet and a so-called primary gas outlet elongated, parallel to the axis and substantially diametrically opposite, said outlet gas emerging inside said tunnel or assembly, said tunnel or assembly being provided with at least one means for injecting a so-called adjacent gas which does not have transited by the said device (s), the
  • heating means infrared lamps red in the tunnel, or convection heating (hot walls of the tunnel) or the fact that the part is placed on a heating substrate holder.
  • the conveyor system 2 passes through an interior space 31, delimited by a tunnel 3, advantageously tightly connected to the device 4.
  • the primary gas mixture obtained at the outlet of the apparatus 6 is shown diagrammatically at 8.
  • the primary gas mixture 8 is obtained from an initial gas mixture 7 entering in the appliance at its gas inlet 5.
  • the gaseous atmosphere comprising the adjacent gas mixtures 9, 10 and the primary gas mixture 8 constitutes the treatment atmosphere 30 according to the invention.
  • the installation can then be completed by other gas mixture inlets adjacent such as those shown in 13 and 29.
  • the installation is also provided, where appropriate, with a heating means for part 1, not shown in FIG. 1.
  • a heating means for part 1 not shown in FIG. 1.
  • the apparatus for this embodiment is of cylindrical geometry, it comprises a first electrode tubular 14, formed for example by an internal face of a metal block 15, and in which is concentrically arranged a set of a tube of dielectric material 16, for example ceramic, on the internal face of which is deposited, by metallization, a second electrode 17, excessively thickened in FIG. 2 for a better understanding.
  • the assembly of the dielectric 16 and of the second electrode 17 thus defined, with the first electrode 14, a tubular gas passage 18, and, internally, a volume internal 19 in which a coolant is circulated, advantageously a Freon for its electronegative character, or even permuted water.
  • the internal gas passage 18 has an axial extension of less than 1 m, typically less than 50 cm, and its radial thickness e does not exceed 3 mm and is typically less than 2.5 mm.
  • the block 15 comprises, diametrically opposite, two longitudinal slots 20 and 21 respectively forming the entry of the initial gas to be excited in the passage 18 and the exit from the primary gas flow comprising excited or unstable gas species.
  • the slots 20 and 21 extend over the entire axial length of the cavity 18 and have a height which, for the embodiment shown, does not exceed the thickness e and is typically substantially identical to the latter.
  • the body 15 advantageously comprises, at the periphery of the first electrode 14, a plurality of conduits 22 for the passage of a refrigerant, for example water.
  • the gas inlet 20 communicates with a homogenization chamber or plenum 23 formed in a housing 24 attached to the block 15 and comprising a pipe 25 for supplying initial gas, at a pressure of between 0.1 ⁇ 10 5 Pa and 3 x 10 5 Pa, coming from an initial gas source 26.
  • the electrodes 14 and 17 are connected to a high voltage and high frequency electric generator 27, operating at a frequency advantageously greater than 15 kHz, delivering a power for example of the order of 10 kW.
  • a high voltage and high frequency electric generator 27 operating at a frequency advantageously greater than 15 kHz, delivering a power for example of the order of 10 kW.
  • the gas flow containing the excited species, available at the gas outlet 21, is addressed to a user station 28, for example for surface treatment metallic.
  • the facility included a single gaseous species forming apparatus excited or unstable in 4, such as that described in connection with FIG. 2.
  • cold rolled low carbon steel sheets were treated 0.2 mm thick.
  • the treated samples were square (10 cm side).
  • the treatment atmosphere used included the addition of an adjacent mixture consisting of nitrogen, and a primary gas mixture obtained from an initial mixture nitrogen / hydrogen to 40% hydrogen.
  • the initial mixture was obtained by respective flow rates of nitrogen and hydrogen of 10 m 3 / h and 7 m 3 / h.
  • the steel pieces were brought to a temperature of 150 ° C. by means of a heating substrate holder.
  • the pressure inside the tunnel was maintained substantially at atmospheric pressure.
  • the energy density used per square centimeter of dielectric was 15 W / cm 2 .
  • the distance between the part and the gas outlet of the device was 10 mm.

Description

La présente invention concerne les étapes de préparation ou traitement de surfaces métalliques intervenant au cours des procédés de production ou de valorisation de produits plats (comme des tôles métalliques) ou corps creux (bouteilles, vannes...).The present invention relates to the stages of preparation or treatment of metal surfaces involved in the production or production processes recovery of flat products (such as metal sheets) or hollow bodies (bottles, valves ...).

Selon l'endroit de la chaíne de fabrication de ces produits où ces étapes interviennent, ces étapes de préparation réalisent des fonctions de nettoyage, de dégraissage ou encore d'activation de la surface, souvent avant un procédé ultérieur, qui peut être par exemple un recuit, l'électrodéposition de zinc, d'aluminium, d'étain ou de leurs alliages ou encore le dépôt de revêtements organiques tels vernis ou peintures, ou inorganiques tels nitrures ou films à base de silicium.Depending on the location of the manufacturing chain of these products where these stages intervene, these preparation stages perform cleaning, degreasing or activation of the surface, often before a subsequent process, which can be, for example, annealing, electroplating zinc, aluminum, tin or their alloys or the deposition of organic coatings such as varnishes or paints, or inorganic such as nitrides or films based on silicon.

Une telle étape de préparation de surfaces pourra aussi intervenir en bout de chaíne, par exemple juste avant la mise en bobines de telles tôles métalliques.Such a surface preparation step may also take place at the end of chain, for example just before coiling such metal sheets.

Selon la destination finale des produits (par exemple l'automobile, l'électroménager, le bâtiment ou encore l'emballage tel que les boites de conserve), les produits concernées sont en acier, en acier inoxydable, en cuivre ou encore par exemple en aluminium.Depending on the final destination of the products (for example the automobile, household appliances, building or packaging such as cans), affected products are steel, stainless steel, copper or by aluminum example.

Parmi les méthodes les plus couramment utilisées pour effectuer ces opérations de préparation de surfaces, on trouve en tout premier lieu des méthodes en phase liquide.Among the most commonly used methods to perform these operations of surface preparation, we find first of all methods in phase liquid.

On peut citer dans cette catégorie, le cas d'une étape préliminaire de dégraissage effectuée à l'aide de solvants, le plus souvent chlorés ou fluorés (faisant actuellement l'objet de réglementation très stricte), ou encore l'exemple des méthodes consistant à dégraisser la surface métallique dans un bain chimique en milieu aqueux contenant des produits acides, alcalins ou encore neutres, qui présentent des inconvénients liés au retraitement nécessaire des eaux usées après nettoyage.We can cite in this category, the case of a preliminary degreasing step performed using solvents, most often chlorinated or fluorinated (currently subject to very strict regulations), or the example of the methods of degrease the metal surface in a chemical bath in an aqueous medium containing acidic, alkaline or even neutral products, which have drawbacks related to necessary reprocessing of wastewater after cleaning.

Dans ce contexte, une deuxième catégorie de méthodes de traitement ou préparation de surfaces métalliques a fait son apparition, elles sont qualifiées de "méthodes par voie sèche". Dans cette catégorie, on peut citer l'exemple du nettoyage de surfaces par plasma gazeux sous basse pression, en utilisant une décharge électrique. Cette méthode est en première approche très attractive, car elle présente l'avantage d'un très bon respect de l'environnement. Elle conjugue deux actions distinctes de la décharge électrique : d'une part, le bombardement ionique intense induit dans certaines conditions par le milieu ionisé, on assiste alors à une action de nettoyage par pulvérisation; d'autre part, la méthode met à contribution la forte réactivité des atomes et des molécules excités présents dans le plasma pour venir former des composés volatils avec les corps à éliminer présents à la surface de la tôle, on assiste alors à une action chimique sur des corps à caractère essentiellement organique. L'atmosphère gazeuse généralement préférée pour cette méthode de décapage sous décharge électrique contient un fort pourcentage d'argon pour sa qualité de gaz fortement plasmagène et pour la masse élevée de ses ions qui rend ce gaz propice à l'action de pulvérisation, elle est par ailleurs enrichie d'oxygène ou encore d'hydrogène pour tirer partie de l'action chimique de la décharge en éliminant les corps à caractère organique présents à la surface de la tôle par formation de composés légers du type COx ou CHy.In this context, a second category of methods of treatment or preparation of metallic surfaces has appeared, they are qualified as "dry methods". In this category, we can cite the example of cleaning surfaces by gaseous plasma under low pressure, using an electric discharge. This method is very attractive at first, because it has the advantage of being very environmentally friendly. It combines two distinct actions of the electric discharge: on the one hand, the intense ion bombardment induced in certain conditions by the ionized medium, one then attends a cleaning action by spraying; on the other hand, the method makes use of the high reactivity of the excited atoms and molecules present in the plasma to come and form volatile compounds with the bodies to be eliminated present on the surface of the sheet, we are then witnessing a chemical action on essentially organic bodies. The generally preferred gaseous atmosphere for this method of pickling under electric discharge contains a high percentage of argon for its quality of highly plasmagenic gas and for the high mass of its ions which makes this gas suitable for spraying action, it is moreover enriched with oxygen or even hydrogen to take advantage of the chemical action of the discharge by eliminating the organic bodies present on the surface of the sheet by the formation of light compounds of the CO x or CH y type .

La forte potentialité de ce procédé ne peut occulter ses inconvénients majeurs liés au fait qu'elle est pratiquée sous pression réduite, voire sous vide. Ces conditions de pression constituent incontestablement un frein à son développement, car elles sont relativement incompatibles avec le traitement de grandes surfaces métalliques ou encore avec des cadences de production élevées (comme c'est le cas des productions industrielles de tôles).The high potential of this process cannot hide its major drawbacks to the fact that it is performed under reduced pressure, or even under vacuum. These conditions of pressure undoubtedly hamper its development, because they are relatively incompatible with the treatment of large metal surfaces or still with high production rates (as is the case with productions sheet metal).

La mise en place de telles basses pressions représente par ailleurs un surcoût non négligeable.The implementation of such low pressures also represents an additional cost not negligible.

Dans un contexte plus général, la demanderesse a , dans la demande de brevet français publiée sous le n° 2,697,456, proposé un procédé de fluxage plasma de surfaces métalliques avant brasage ou étamage, à la pression atmosphérique, utilisant pour créer le plasma une source de micro-ondes ou encore une décharge couronne transférée via des lumières placées de façon adéquate dans une couche diélectrique située au-dessus de la pièce à traiter.In a more general context, the applicant has, in the patent application French published under No. 2,697,456, proposed a plasma fluxing process of metal surfaces before brazing or tinning, at atmospheric pressure, using to create the plasma a microwave source or a corona discharge transferred via lights suitably placed in a dielectric layer located above the part to be treated.

Si cette demande apporte une réponse intéressante au problème du fluxage de surfaces métalliques, la Demanderesse a mis en évidence le fait que le procédé proposé pourrait être amélioré, notamment en ce qui concerne :

  • son rendement (rapport de la puissance introduite pour créer le plasma à la densité d'espèces produites qui interagissent effectivement avec le support à traiter), ou encore la densité d'énergie obtenue (dans le cas de la décharge couronne, elle n'atteint que quelques W par unité de surface de diélectrique), qui si ils étaient accrus pourraient permettre des temps de traitement plus courts,
  • mais aussi du fait de facteurs "géométriques" limitants : dans le cas de la décharge couronne traditionnelle, la distance électrode/échantillon est tout à fait critique et doit être maintenue très faible, ce qui peut poser problème dans le cas de substrats dont le relief est relativement tourmenté; dans le cas de la décharge micro-ondes, elle donne lieu à la formation d'un spot plasmagène, de dimensions déterminées et limitées par la source plasma,
  • par ailleurs, un plasma tel que celui créé dans ce document, contient par définition des espèces ioniques et des électrons (donc des espèces électriquement chargées) pouvant induire un bombardement ionique et donc un effet de pulvérisation de la surface métallique qui dans certains cas, peut s'avérer préjudiciable (par exemple quand la surface métallique est recouverte d'un revêtement que l'on ne souhaite pas altérer).
If this request provides an interesting answer to the problem of the fluxing of metal surfaces, the Applicant has highlighted the fact that the proposed process could be improved, in particular as regards:
  • its efficiency (ratio of the power introduced to create the plasma to the density of produced species which actually interact with the support to be treated), or the energy density obtained (in the case of corona discharge, it does not reach than a few W per unit of dielectric surface), which if increased could allow shorter treatment times,
  • but also due to limiting "geometric" factors: in the case of traditional crown discharge, the electrode / sample distance is quite critical and must be kept very small, which can be problematic in the case of substrates whose relief is relatively tormented; in the case of microwave discharge, it gives rise to the formation of a plasma spot, of dimensions determined and limited by the plasma source,
  • moreover, a plasma such as that created in this document, by definition contains ionic species and electrons (therefore electrically charged species) which can induce ionic bombardment and therefore a sputtering effect on the metallic surface which in certain cases can prove to be harmful (for example when the metal surface is covered with a coating which one does not wish to alter).

En parallèle, la demanderesse a proposé dans la demande de brevet français publiée sous le n° 2,692,730, un dispositif de formation de molécules gazeuses excitées ou instables fonctionnant sensiblement à la pression atmosphérique.In parallel, the applicant proposed in the French patent application published under No. 2,692,730, a device for forming excited or unstable gas molecules operating substantially at atmospheric pressure.

On se reportera également au document EP-A-305 241, qui s'intéresse aux traitements thermiques de nitruration, carburation, boruration ou oxydation de pièces métalliques, par mise en contact directe, au sein d'une chambre réactionnelle, entre le substrat à traiter et une atmosphère obtenue en aval d'un plasma.Reference will also be made to document EP-A-305 241, which is concerned with treatments thermal nitriding, carburizing, boriding or oxidation of metallic parts, by direct contact, within a reaction chamber, between the substrate to be treated and a atmosphere obtained downstream of a plasma.

Dans ce contexte, la présente invention a pour objet de proposer un procédé amélioré de traitement de surfaces métalliques par voie sèche, permettant:

  • d'opérer sensiblement à pression atmosphérique,
  • une grande flexibilité de distance entre l'objet à traiter et le dispositif utilisé pour effectuer ce traitement,
  • d'éviter le contact des pièces avec des espèces électriquement chargées,
  • d'offrir une densité énergétique améliorée permettant une vitesse de traitement accrue.
In this context, the object of the present invention is to propose an improved method for treating metallic surfaces by the dry route, making it possible:
  • to operate substantially at atmospheric pressure,
  • great flexibility of distance between the object to be treated and the device used to perform this treatment,
  • avoid contact of the parts with electrically charged cash,
  • to offer an improved energy density allowing an increased processing speed.

Pour ce faire, le procédé de traitement de surfaces par voie sèche d'au moins une portion de surface métallique, selon l'invention, se caractérise par le fait que la portion de surface métallique est traitée, à une pression voisine de la pression atmosphérique, par une atmosphère gazeuse de traitement comprenant des espèces excitées ou instables et étant substantiellement dépourvue d'espèces électriquement chargées.To do this, the method of treating surfaces by the dry route of at least one portion of metal surface, according to the invention, is characterized in that the portion of metal surface is treated, at a pressure close to atmospheric pressure, by a treatment gas atmosphere comprising excited species or unstable and being substantially free of electrically charged species.

On entend par "surface métallique" selon l'invention, tout type de surface, qu'elle soit par exemple en acier, en inox, en cuivre, ou encore en aluminium, quelque soit la dimension ou l'épaisseur de la pièce comportant la ou les portions de surface métallique à traiter. Leur application industrielle finale peut être très variée, que ces surfaces métalliques soient par exemple utilisées dans le domaine de l'électroménager, de l'automobile, des gaz industriels ou encore dans l'industrie du bâtiment ou de l'emballage.The term “metallic surface” according to the invention means any type of surface, whether it either for example steel, stainless steel, copper, or aluminum, whatever the dimension or thickness of the part comprising the surface portion (s) metal to be treated. Their final industrial application can be very varied, whether these metal surfaces are for example used in the field of household appliances, automotive, industrial gases or in the building industry or packaging.

On entend par l'expression "traitement de surface" selon l'invention, toute étape de préparation, nettoyage, activation ou encore dégraissage de la portion de surface métallique, cette étape pouvant intervenir à des endroits très divers de la chaíne de fabrication des produits utilisant de telles surfaces métalliques (qu'ils soient plats tels que par exemple des tôles, ou creux tels que par exemple des bouteilles), cette étape pouvant intervenir en bout de chaíne (avant par exemple la mise en bobine de telles tôles métalliques) ou encore en cours de fabrication, avant un procédé ultérieur, qui peut être par exemple un recuit, une opération telle que l'électrodéposition de zinc, d'aluminium, d'étain ou de leurs alliages, ou encore le dépôt de revêtements organiques tels qu'un vernis ou une peinture, ou inorganiques tels nitrure ou films à base de silicium.The expression "surface treatment" according to the invention means any step preparation, cleaning, activation or degreasing of the surface portion metallic, this step being able to intervene in very different places of the chain of manufacture of products using such metal surfaces (whether flat as that for example sheets, or hollow such as for example bottles), this step can intervene at the end of the chain (before for example the rewinding of such metal sheets) or during production, before a subsequent process, which may for example be an annealing, an operation such as zinc plating, aluminum, tin or their alloys, or the deposition of organic coatings such as varnish or paint, or inorganic such as nitride or films based on silicon.

L'application du procédé de traitement de surface selon l'invention aura alors notamment pour objectif de faciliter l'application du procédé ultérieur, par exemple, faciliter l'accrochage d'un revêtement de peinture.The application of the surface treatment method according to the invention will then have in particular to facilitate the application of the subsequent process, for example, facilitate the attachment of a paint coating.

L'application du procédé de traitement de surface selon l'invention pourra alors intervenir seule ou en complément d'une autre méthode de préparation de surface, effectuée antérieurement ou postérieurement à l'application du procédé selon l'invention.The application of the surface treatment method according to the invention can then intervene alone or in addition to another surface preparation method, performed before or after the application of the process according to the invention.

On entend par le terme "pression voisine de la pression atmosphérique" selon l'invention une pression qui se situe dans l'intervalle [0,1 x 105 Pa, 3 x 105 Pa].The term "pressure close to atmospheric pressure" according to the invention means a pressure which lies in the range [0.1 × 10 5 Pa, 3 × 10 5 Pa].

L'atmosphère de traitement selon l'invention se distingue des atmosphères plasma classiques par le fait qu'elle est substantiellement dépourvue d'espèces électriquement chargées, c'est à dire d'ions où d'électrons.The treatment atmosphere according to the invention is distinguished from plasma atmospheres classics by the fact that it is substantially devoid of cash electrically charged, ie ions or electrons.

L'atmosphère gazeuse de traitement est obtenue à partir d'un mélange gazeux primaire et d'un mélange gazeux adjacent, le mélange gazeux primaire étant obtenu à la sortie de gaz d'au moins un appareil de formation d'espèces gazeuses excitées ou instables dans lequel a été transformé un mélange gazeux initial comprenant un gaz inerte et/ou un gaz réducteur et/ou un gaz oxydant, le mélange adjacent n'ayant pas transité par l'appareil.The treatment gas atmosphere is obtained from a gas mixture primary and an adjacent gas mixture, the primary gas mixture being obtained at the gas outlet of at least one apparatus for forming gaseous species excited or unstable in which an initial gas mixture has been transformed comprising an inert gas and / or a reducing gas and / or an oxidizing gas, the mixture adjacent having not passed through the device.

L' appareil selon l'invention est constitué par tout dispositif permettant "d'exciter" un mélange gazeux initial, pour obtenir, en sortie de gaz de l'appareil, un autre mélange gazeux comportant des espèces gazeuses instables ou excitées, ce dernier mélange gazeux étant substantiellement dépourvu d'espèces électriquement chargées, une telle excitation étant obtenue par décharge électrique, par exemple du type décharge couronne.The apparatus according to the invention is constituted by any device allowing "to excite" an initial gas mixture, to obtain, at the gas outlet of the device, another gas mixture comprising unstable or excited gaseous species, the latter gas mixture being substantially free of electrically charged species, such an excitation being obtained by electric discharge, by example of the crown discharge type.

On peut qualifier cette configuration de "post-décharge" puisque la composante primaire de l'atmosphère de traitement, qui comprend des espèces gazeuses excitées ou instables, est obtenue en sortie d' appareil, ce qui assure l'absence substancielle de toute espèce électriquement chargée dans cette composante primaire. La composante adjacente de l'atmosphère de traitement, qui n'a pas transité par l'appareil, en est à fortiori dépourvue.This configuration can be described as "post-discharge" since the primary component of the treatment atmosphere, which includes excited or unstable gaseous species, is obtained at the device outlet , which ensures the substantial absence of any species electrically. loaded into this primary component. The adjacent component of the treatment atmosphere, which has not passed through the device, is a fortiori devoid of it.

Par ailleurs, cette configuration permet de nettement séparer le lieu de la génération de la composante primaire de l'atmosphère du lieu de son utilisation, ce qui présente un avantage non négligeable en terme de pollution de l'appareil (éviter que les dégagements divers résultant de l'opération de traitement de surface n'aillent polluer l'intérieur de l'appareil, par exemple ses électrodes). Enfin, la pièce, qui n'est pas traitée au sein de l'appareil (par exemple au sein de la décharge entre les électrodes), bénéficie d'une bien meilleure fléxibilité sur l'aspect "distance" évoqué plus haut.Furthermore, this configuration makes it possible to clearly separate the place from the generation of the primary component of the atmosphere of the place of its use, which has a significant advantage in terms of pollution of the device (avoid that various clearances resulting from the surface treatment operation will not pollute inside the device, for example its electrodes). Finally, the play, which is not treated within the device (for example within the discharge between the electrodes), benefits from much better flexibility on the "distance" aspect mentioned above.

Le gaz inerte peut par exemple consister en de l'azote, de l'argon, de l'hélium ou un mélange de tels gaz inertes. Le gaz réducteur peut par exemple consister en de l'hydrogène, du CH4, du gaz naturel, du propane ou encore de l'ammoniac ou un mélange de tels gaz réducteurs. Le gaz oxydant peut quant à lui par exemple consister en de l'oxygène, ou du CO2, ou encore du N2O, H2O ou un mélange de tels gaz oxydants. La liste de gaz donnés dans chaque catégorie n'étant bien entendu qu'indicative, nullement limitative.The inert gas can for example consist of nitrogen, argon, helium or a mixture of such inert gases. The reducing gas can for example consist of hydrogen, CH 4 , natural gas, propane or even ammonia or a mixture of such reducing gases. The oxidizing gas can for example consist of oxygen, or CO 2 , or even N 2 O, H 2 O or a mixture of such oxidizing gases. The list of gases given in each category is of course only indicative, in no way limiting.

Comme il apparaítra clairement à l'homme du métier, le mélange gazeux initial selon l'invention est traité ou transformé dans au moins un appareil de formation d'espèces gazeuses excitées ou instables, de façon à obtenir en sortie de gaz dudit appareil, un mélange gazeux dit primaire comprenant des espèces gazeuses excitées ou instables.As will be clear to those skilled in the art, the initial gas mixture according to the invention is treated or transformed in at least one training device excited or unstable gaseous species, so as to obtain a gas outlet from said gas device, a so-called primary gas mixture comprising excited gas species or unstable.

Comme il apparaítra aussi clairement à l'homme du métier, la pièce comprenant la ou les portions de surfaces à traiter pourra être mise en contact avec le mélange gazeux primaire obtenu en sortie de gaz d'un seul appareil de formation d'espèces gazeuses excitées ou instables ou de plusieurs appareils placés en parallèle sur la largeur de la pièce ou successivement avec les mélanges gazeux primaires obtenus aux sorties de gaz de plusieurs appareils de formation d'espèces gazeuses excitées ou instables placés en série.As will be apparent to those skilled in the art, the part comprising the portion (s) of surfaces to be treated may be brought into contact with the mixture primary gaseous obtained at the gas outlet of a single species-forming apparatus excited or unstable gases or of several devices placed in parallel on the width of the room or successively with the primary gas mixtures obtained at gas outlets from multiple excited gaseous species forming devices or unstable placed in series.

Le procédé selon l'invention s'applique selon les besoins exprimés par l'utilisateur tant au traitement d'une seule des faces de la pièce à traiter, qu'au cas où l'on doit traiter la pièce sur ses deux faces. Dans ce dernier cas, il conviendra de disposer les appareils requis en regard de chaque face de la pièce.The method according to the invention is applied according to the needs expressed by the user both when treating only one side of the part to be treated and when it is necessary treat the part on both sides. In the latter case, the required devices next to each side of the room.

Le mélange adjacent, selon l'invention, pourra être constitué de tout gaz ou mélange de gaz, par exemple d'un gaz inerte ou mélange de gaz inertes permettant de maintenir, le cas échéant, une atmosphère protectrice autour des pièces, ou encore d'un gaz réducteur ou d'un gaz oxydant, voire d'un mélange de gaz appartenant à l'une de ces trois catégories.The adjacent mixture, according to the invention, may consist of any gas or mixture of gases, for example an inert gas or mixture of inert gases making it possible to if necessary, maintain a protective atmosphere around the parts, or reducing gas or an oxidizing gas, or even a mixture of gases belonging to one of these three categories.

Selon un des aspects de l'invention, le mélange adjacent contient du silane SiH4. Un tel mélange adjacent contenant du silane est avantageusement utilisé pour son action réductrice vis-à-vis de certains oxydes métalliques présents à la surface de la pièce, mais aussi, selon le mélange gazeux initial utilisé, comme "guetter" (ou piègeur) d'oxygène, c'est-à-dire dans son interaction avec l'oxygène résiduel de l'atmosphère présente au-dessus de la pièce, dans le but de réduire à un minimum ce niveau d'oxygène résiduel. According to one aspect of the invention, the adjacent mixture contains silane SiH 4 . Such an adjacent mixture containing silane is advantageously used for its reducing action with respect to certain metal oxides present on the surface of the part, but also, depending on the initial gas mixture used, as a "lookout" (or trap). oxygen, that is to say in its interaction with the residual oxygen of the atmosphere present above the room, with the aim of reducing to a minimum this level of residual oxygen.

Selon une des mises en oeuvre de l'invention, la portion de surface métallique à traiter est portée à une température n'excedant pas 600°C, typiquement comprise entre la température ambiante et 600°C.According to one of the embodiments of the invention, the portion of metal surface to process is brought to a temperature not exceeding 600 ° C, typically between room temperature and 600 ° C.

Selon une des mises en oeuvre de l'invention, la pièce comportant la portion à traiter est amenée en regard de la sortie de gaz dudit appareil, le cas échéant en regard des sorties de gaz de plusieurs appareils placés en parallèle sur la largeur de la pièce et/ou successivement en regard des sorties de gaz de plusieurs appareils placés en série, par un système de convoyage traversant un espace intérieur délimité par un tunnel ou un ensemble de capotage, isolé de l'atmosphère environnante, ledit tunnel ou ensemble étant raccordé de façon étanche audit appareil ou incluant le dit appareil.According to one of the embodiments of the invention, the part comprising the portion to to be treated is brought opposite the gas outlet of said device, if necessary opposite gas outlets of several appliances placed in parallel across the width of the room and / or successively opposite the gas outlets of several devices placed in series, by a conveyor system crossing an interior space delimited by a tunnel or a casing assembly, isolated from the surrounding atmosphere, said tunnel or assembly being tightly connected to said device or including said device.

La même remarque déja effectuée plus haut s'applique ici, sur le traitement en double faces (ici encore, il suffit de mettre en oeuvre les appareils requis, en nombre et en disposition, en regard de chaque face de la pièce).The same remark already made above applies here, on the treatment in double-sided (here again, it suffices to install the required devices, in number and available, facing each side of the room).

Le convoyeur selon l'invention pourra, selon l'industrie considérée, par exemple consister en un tapis ou encore dans le cas de tôles métalliques par des rouleaux.The conveyor according to the invention may, depending on the industry considered, for example consist of a carpet or in the case of metal sheets by rollers.

Selon une des mises en oeuvre de l'invention, l'appareil, dans lequel est transformé ledit mélange gazeux initial est le siège d'une décharge électrique créée entre une première électrode et une seconde électrode , une couche d'un matériau diélectrique étant disposée sur la surface d'au moins une des électrodes, en regard de l'autre électrode, le mélange gazeux initial traversant la décharge transversalement aux électrodes.According to one of the embodiments of the invention, the apparatus, in which is transformed said initial gas mixture is the seat of an electrical discharge created between a first electrode and a second electrode, a layer of material being placed on the surface of at least one of the electrodes, facing the other electrode, the initial gas mixture crossing the discharge transversely to the electrodes.

Selon un des aspects de l'invention, l'énergie mise en oeuvre dans l'appareil, ramenée à l'unité de surface de diélectrique sera alors avantageusement supérieure à un 1W/cm2, préférentiellement supérieure à 10W/cm2. According to one aspect of the invention, the energy used in the device, reduced to the dielectric surface unit will then advantageously be greater than 1W / cm 2 , preferably greater than 10W / cm 2.

Selon une des mises en oeuvre de l'invention, on réalise un zonage de l'atmosphère de traitement rencontrée successivement par la pièce à traiter le long du convoyeur, de la façon suivante :

  • a) au moins un des appareils de formation d'espèces gazeuses excitées ou instables, transforme un mélange gazeux initial différent de celui transformé par l'appareil le précédant dans le dit tunnel ou ensemble, et/ou
  • b) le mélange gazeux adjacent mis en oeuvre au niveau d'au moins un des appareils de formation d'espèces gazeuses excitées ou instables est différent de celui mis en oeuvre au niveau de l'appareil le précédant dans le dit tunnel ou ensemble.
    • According to one of the embodiments of the invention, a zoning of the treatment atmosphere met successively by the part to be treated is carried out along the conveyor, as follows:
  • a) at least one of the apparatuses for forming excited or unstable gaseous species transforms an initial gaseous mixture different from that transformed by the apparatus preceding it in said tunnel or together, and / or
  • b) the adjacent gas mixture used in at least one of the apparatuses for forming excited or unstable gaseous species is different from that used in the apparatus preceding it in said tunnel or together.

    • Selon une des mises en oeuvre de l'invention, les étapes a) et b) ci-dessus pourront concerner un même appareil.According to one of the embodiments of the invention, steps a) and b) above may relate to the same device.

    On pourra ainsi par exemple utiliser des mélanges de pouvoir réducteur croissant, d'un appareil à l'autre. It will thus be possible, for example, to use mixtures of increasing reducing power, from one device to another.

    L'invention concerne aussi l'utilisation d'un dispositif de traitement de surface par voie sèche d'au moins une portion de surface métallique, dispositif comprenant un tunnel ou un ensemble de capotage définissant un espace intérieur traversé par des moyens de convoyage des pièces comportant la ou les portions de surfaces à traiter, étanche vis-à-vis de l'atmosphère environnante, se raccordant de façon étanche ou incluant un ou plusieurs appareils de formation d'espèces gazeuses excitées ou instables montés en série et/ou parallèle comprenant au moins un passage de gaz tubulaire ayant un axe, formé entre une électrode extérieure et une électrode intérieure, l'une au moins des électrodes comportant, en regard de l'autre, un revêtement diélectrique, les électrodes étant reliées à une source haute tension et haute fréquence, l'électrode extérieure entourant le diélectrique et comportant une entrée de gaz dit initial et une sortie de gaz dit primaire allongées, parallèles à l'axe et sensiblement diamétralement opposées, ladite sortie de gaz débouchant à l'intérieur dudit tunnel ou ensemble, le dit tunnel ou ensemble étant muni d'au moins un moyen d'injection d'un gaz dit adjacent n'ayant pas transité par le ou les dits appareils, le dispositif comprenant de plus, le cas échéant, un moyen de chauffage des pièces à traiter.The invention also relates to the use of a dry surface treatment device at least a portion of metal surface, device comprising a tunnel or a casing assembly defining an interior space traversed by means of conveying the pieces comprising the portion (s) of surfaces to be treated, airtight vis-à-vis the atmosphere surrounding area, sealingly connected or including one or more formation of excited or unstable gas species mounted in series and / or parallel comprising at least one tubular gas passage having an axis, formed between a external electrode and an internal electrode, at least one of the electrodes comprising, facing each other, a dielectric coating, the electrodes being connected to a high voltage and high frequency source, the outer electrode surrounding the dielectric and comprising a so-called initial gas inlet and a so-called primary gas outlet elongated, parallel to the axis and substantially diametrically opposite, said outlet gas emerging inside said tunnel or assembly, said tunnel or assembly being provided with at least one means for injecting a so-called adjacent gas which does not have transited by the said device (s), the device further comprising, where appropriate, a means of heating the parts to be treated.

    On pourra par exemple envisager, pour ce moyen de chauffage, des lampes infra rouge présentes dans le tunnel, ou un chauffage par convection (parois chaudes du tunnel) ou encore le fait que la pièce soit posée sur un porte-substrat chauffant.We can for example consider, for this heating means, infrared lamps red in the tunnel, or convection heating (hot walls of the tunnel) or the fact that the part is placed on a heating substrate holder.

    D'autres caractéristiques et avantages de la présente invention ressortiront de la description suivante de modes de réalisation, donnés à titre illustratif mais nullement limitatif, faits en relation avec les dessins annexés sur lesquels :

    • la figure 1 est une vue schématique d'une installation convenant pour la mise en oeuvre du procédé selon l'invention.
    • la figure 2 représente schématiquement en coupe un exemple d'appareil de formation d'espèces gazeuses excitées ou instables convenant pour la mise en oeuvre du procédé selon l'invention.
    Other characteristics and advantages of the present invention will emerge from the following description of embodiments, given by way of illustration but in no way limiting, made in relation to the appended drawings in which:
    • Figure 1 is a schematic view of an installation suitable for implementing the method according to the invention.
    • FIG. 2 schematically shows in section an example of an apparatus for forming excited or unstable gaseous species suitable for implementing the method according to the invention.

    On reconnaít sur la figure 1, la présence d'une pièce 1 comportant la ou les portions de surface métalliques à traiter, amenée grâce à un moyen de convoyage 2, en regard de la sortie de gaz 6 d'un appareil 4 de formation d'espèces gazeuses excitées ou instables.We recognize in Figure 1, the presence of a part 1 comprising the or metal surface portions to be treated, brought in by a conveying means 2, in sight of the gas outlet 6 of an apparatus 4 for forming excited gaseous species or unstable.

    Le système de convoyage 2 traverse un espace intérieur 31, délimité par un tunnel 3, raccordé avantageusement de façon étanche à l'appareil 4.The conveyor system 2 passes through an interior space 31, delimited by a tunnel 3, advantageously tightly connected to the device 4.

    On a schématisé en 8 le mélange gazeux primaire obtenu en sortie de l'appareil 6. Le mélange gazeux primaire 8 est obtenu à partir d'un mélange gazeux initial 7 entrant dans l'appareil au niveau de son entrée de gaz 5. The primary gas mixture obtained at the outlet of the apparatus 6 is shown diagrammatically at 8. The primary gas mixture 8 is obtained from an initial gas mixture 7 entering in the appliance at its gas inlet 5.

    On note aussi sur le mode de réalisation représenté sur la figure 1 la présence d'entrées de mélanges gazeux adjacents 9, 10. L'atmosphère gazeuse comprenant les mélanges gazeux adjacents 9, 10 et le mélange gazeux primaire 8 constitue l'atmosphère de traitement 30 selon l'invention.We also note on the embodiment shown in Figure 1 the presence inputs of adjacent gas mixtures 9, 10. The gaseous atmosphere comprising the adjacent gas mixtures 9, 10 and the primary gas mixture 8 constitutes the treatment atmosphere 30 according to the invention.

    On note sur le mode de réalisation représenté sur la figure 1, la présence d'appareils de formation d'espèces gazeuses excitées ou instables supplémentaires, non représentés, en 11 et 12, en série avec le premier appareil 4 et que rencontre successivement la pièce 1.We note on the embodiment shown in Figure 1, the presence apparatus for forming excited or unstable additional gaseous species, not represented, in 11 and 12, in series with the first device 4 and that meets successively piece 1.

    L'installation peut se compléter alors par d'autres entrées de mélanges de gaz adjacents telles que celles représentées en 13 et 29.The installation can then be completed by other gas mixture inlets adjacent such as those shown in 13 and 29.

    L'installation est par ailleurs pourvue, le cas échéant, d'un moyen de chauffage de la pièce 1, non représenté sur la figure 1. On pourra par exemple envisager, pour ce moyen de chauffage, des lampes infra rouge présentes dans le tunnel, ou un chauffage par convection (parois chaudes du tunnel) ou encore le fait que la pièce soit posée sur un porte-substrat chauffant.The installation is also provided, where appropriate, with a heating means for part 1, not shown in FIG. 1. We could for example consider, for this means of heating, infrared lamps present in the tunnel, or heating by convection (hot walls of the tunnel) or the fact that the part is placed on a heating substrate holder.

    Comme représenté sur le mode de réalisation de la figure 2, l'appareil pour ce mode de réalisation est de géométrie cylindrique, il comprend une première électrode tubulaire 14, formée par exemple par une face interne d'un bloc métallique 15, et dans laquelle est disposé concentriquement un ensemble d'un tube en matériau diélectrique 16, par exemple en céramique, sur la face interne duquel est déposée, par métallisation, une deuxième électrode 17, exagérément épaissie sur la figure 2 pour une meilleure compréhension.As shown in the embodiment of Figure 2, the apparatus for this embodiment is of cylindrical geometry, it comprises a first electrode tubular 14, formed for example by an internal face of a metal block 15, and in which is concentrically arranged a set of a tube of dielectric material 16, for example ceramic, on the internal face of which is deposited, by metallization, a second electrode 17, excessively thickened in FIG. 2 for a better understanding.

    L'ensemble du diélectrique 16 et de la deuxième électrode 17 défini ainsi, avec la première électrode 14, un passage tubulaire de gaz 18, et, intérieurement, un volume interne 19 dans lequel on fait circuler un réfrigérant, avantageusement un Fréon pour son caractère électronégatif, ou encore de l'eau permutée. Le passage de gaz interne 18 a une extension axiale inférieure à 1 m, typiquement inférieure à 50 cm, et son épaisseur radiale e n'excède pas 3 mm et est typiquement inférieure à 2,5 mm.The assembly of the dielectric 16 and of the second electrode 17 thus defined, with the first electrode 14, a tubular gas passage 18, and, internally, a volume internal 19 in which a coolant is circulated, advantageously a Freon for its electronegative character, or even permuted water. The internal gas passage 18 has an axial extension of less than 1 m, typically less than 50 cm, and its radial thickness e does not exceed 3 mm and is typically less than 2.5 mm.

    Le bloc 15 comporte, diamétralement opposées, deux fentes longitudinales 20 et 21 formant respectivement l'entrée du gaz initial à exciter dans le passage 18 et la sortie du flux de gaz primaire comportant des espèces gazeuses excitées ou instables.The block 15 comprises, diametrically opposite, two longitudinal slots 20 and 21 respectively forming the entry of the initial gas to be excited in the passage 18 and the exit from the primary gas flow comprising excited or unstable gas species.

    Les fentes 20 et 21 s'étendent sur toute la longueur axiale de la cavité 18 et ont une hauteur qui, pour le mode de réalisation représenté, n'excède pas l'épaisseur e et est typiquement sensiblement identique à cette dernière. Le corps 15 comporte avantageusement, à la périphérie de la première électrode 14, une pluralité de conduits 22 pour le passage d'un réfrigérant, par exemple de l'eau. L'entrée de gaz 20 communique avec une chambre ou plénum d'homogénéisation 23 formée dans un boítier 24 accolé au bloc 15 et comportant une tubulure 25 d'amenée de gaz initial, à une pression comprise entre 0,1 x 105Pa et 3 x 105 Pa, en provenance d'une source de gaz initial 26. Les électrodes 14 et 17 sont reliées à un générateur électrique haute tension et haute fréquence 27, fonctionnant à une fréquence avantageusement supérieure à 15 kHz, délivrant une puissance par exemple de l'ordre de 10 kW. On pourra d'ailleurs avantageusement exprimer cette puissance délivrée par le générateur en la ramenant à la surface de diélectrique (donc à l'unité de surface de l'électrode diélectrique).The slots 20 and 21 extend over the entire axial length of the cavity 18 and have a height which, for the embodiment shown, does not exceed the thickness e and is typically substantially identical to the latter. The body 15 advantageously comprises, at the periphery of the first electrode 14, a plurality of conduits 22 for the passage of a refrigerant, for example water. The gas inlet 20 communicates with a homogenization chamber or plenum 23 formed in a housing 24 attached to the block 15 and comprising a pipe 25 for supplying initial gas, at a pressure of between 0.1 × 10 5 Pa and 3 x 10 5 Pa, coming from an initial gas source 26. The electrodes 14 and 17 are connected to a high voltage and high frequency electric generator 27, operating at a frequency advantageously greater than 15 kHz, delivering a power for example of the order of 10 kW. We can also advantageously express this power delivered by the generator by reducing it to the dielectric surface (therefore to the surface unit of the dielectric electrode).

    Le flux gazeux contenant les espèces excitées, disponible à la sortie de gaz 21, est adressé à un poste utilisateur 28, par exemple pour le traitement de surfaces métalliques.The gas flow containing the excited species, available at the gas outlet 21, is addressed to a user station 28, for example for surface treatment metallic.

    Une installation telle que celle décrite en relation avec la figure 1 a été utilisée pour la réalisation d'un exemple de mise en oeuvre de l'invention.An installation such as that described in connection with FIG. 1 was used for the production of an exemplary implementation of the invention.

    L'installation comprenait un seul appareil de formation d'espèces gazeuses excitées ou instables en 4, tel que celui décrit en relation avec la figure 2. Pour cet exemple de mise en oeuvre, on a traité des tôles d'acier bas carbone laminées à froid de 0,2 mm d'épaisseur. Les échantillons traités étaient de forme carrée (de 10 cm de côté).The facility included a single gaseous species forming apparatus excited or unstable in 4, such as that described in connection with FIG. 2. For this example of implementation, cold rolled low carbon steel sheets were treated 0.2 mm thick. The treated samples were square (10 cm side).

    L'atmosphère de traitement utilisée comportait l'apport d'un mélange adjacent constitué d'azote, et un mélange gazeux primaire obtenu à partir d'un mélange initial azote/hydrogène à 40 % d'hydrogène.The treatment atmosphere used included the addition of an adjacent mixture consisting of nitrogen, and a primary gas mixture obtained from an initial mixture nitrogen / hydrogen to 40% hydrogen.

    Le mélange initial était obtenu par des débits respectifs en azote et en hydrogène de 10 m3/h et 7 m3/h. Durant le traitement, les pièces d'acier étaient portées à une température de 150°C par l'intermédiaire d'un porte-substrat chauffant. La pression à l'intérieur du tunnel était maintenue sensiblement au niveau de la pression atmosphérique. La densité d'énergie mise en oeuvre par centimètre carré de diélectrique était de 15 W/cm2. La distance entre la pièce et la sortie de gaz de l'appareil était de 10 mm.The initial mixture was obtained by respective flow rates of nitrogen and hydrogen of 10 m 3 / h and 7 m 3 / h. During the treatment, the steel pieces were brought to a temperature of 150 ° C. by means of a heating substrate holder. The pressure inside the tunnel was maintained substantially at atmospheric pressure. The energy density used per square centimeter of dielectric was 15 W / cm 2 . The distance between the part and the gas outlet of the device was 10 mm.

    Chaque pièce d'acier était traitée au défilé, grâce au moyen de convoyage 2, en 2 mn. La qualité du nettoyage de surface ainsi obtenu a été testée par un dépôt ultérieur de silice dont on a évalué l'adhérence sur les pièces d'acier ainsi traitées. On a évalué l'adhérence d'un dépôt de 5.000 Angström de silice sur de telles pièces d'acier par la méthode dite "du scotch" représentant un test classique dans la profession.Each piece of steel was treated on parade, using conveyor 2, in 2 min. The quality of the surface cleaning thus obtained was tested by a subsequent deposit. silica whose adhesion was evaluated on the steel parts thus treated. We evaluated the adhesion of a deposit of 5,000 Angstroms of silica on such pieces of steel by the method called "scotch" representing a classic test in the profession.

    Le test du scotch a été ici appliqué de la façon suivante :

    • le dépôt de silice a été effectué, et gravé de façon à créer 100 carreaux sur une surface de 1 cm2 de l'échantillon d'acier (de 10 cm par 10 cm), chaque carreau ayant une surface approximative de 1 mm2. Après dépôt, un ruban adhésif était collé proprement sur ce cm2 de la surface de l'échantillon de tôle, puis décollé. Le test consistait alors à compter les carreaux arrachés et fixés sur la face intérieure du ruban. Les résultats obtenus après nettoyage de surface comme précédemment décrit dans cet exemple de mise en oeuvre ont montré un résultat de 100 % de carreaux de silice demeurant en place sur chaque pièce de tôle métallique correspondant à un arrachage de zéro carreau sur la face intérieure du ruban. Ce résultat est à comparer avec le cas où la pièce métallique n'a pas été nettoyée par le procédé selon l'invention, elle a simplement été dégraissée à l'aide d'un solvant tel que l'hexane. On obtient alors pour ces pièces métalliques non traitées un résultat de 100 % de carreaux arrachés, correspondant à zéro carreau de silice demeurant en place sur la pièce métallique.
    The scotch test was applied here as follows:
    • the deposition of silica was carried out, and etched so as to create 100 tiles on an area of 1 cm 2 of the steel sample (10 cm by 10 cm), each tile having an approximate area of 1 mm 2 . After deposition, an adhesive tape was stuck cleanly on this cm 2 of the surface of the sheet sample, then peeled off. The test then consisted in counting the tiles torn off and fixed on the inside of the ribbon. The results obtained after surface cleaning as previously described in this example of implementation have shown a result of 100% of silica tiles remaining in place on each piece of metal sheet corresponding to a tearing of zero tiles on the inside of the ribbon. . This result should be compared with the case where the metal part has not been cleaned by the method according to the invention, it has simply been degreased using a solvent such as hexane. We then obtain for these untreated metal parts a result of 100% torn tiles, corresponding to zero silica tiles remaining in place on the metal part.

    Quoique la présente invention ait été décrite en relation avec des modes de réalisation particuliers, elle ne s'en trouve pas limitée pour autant mais est au contraire susceptible de modifications et de variantes qui apparaítront à la l'homme de l'art dans le cadre des revendications ci-après.Although the present invention has been described in relation to modes of particular realization, it is not limited for all that but is on the contrary susceptible of modifications and variants which will appear to those skilled in the art in the scope of the claims below.

    Claims (10)

    1. Process for the dry surface preparation of at least one metal surface portion with the aim of performing one or more of the following functions on the said metal surface: cleaning, degreasing, surface activation,
         characterized in that the portion is treated, at a pressure close to atmospheric pressure, by a gaseous treatment atmosphere comprising excited or unstable species and substantially devoid of electrically charged species, obtained from:
      a primary gaseous mixture (8), which is obtained at the gas outlet (6) of at least one device (4) for the production of excited or unstable gaseous species, in which an initial gaseous mixture (7) comprising an inert gas and/or a reducing gas and/or an oxidizing gas has been converted by electric discharge; and
      from an adjacent gaseous mixture (9, 10) not having passed through the said device (4).
    2. Process according to Claim 1, characterized in that the adjacent gaseous mixture is a reducing mixture.
    3. Process according to Claim 1 or 2, characterized in that the adjacent gaseous mixture contains silane SiH4.
    4. Process according to one of Claims 1 to 3, characterized in that the component including the metal portion to be treated is brought to a temperature of no more than 600°C.
    5. Process according to one of Claims 1 to 4, characterized in that the component (1) including the metal portion to be treated is brought opposite the gas outlet (6) of the said device (4), if necessary opposite the gas outlets of a plurality of devices arranged in parallel over the width of the component and/or successively opposite the gas outlets of a plurality of devices (11, 4, 12) arranged in series, by a conveying system (2) traversing an inner space (31) delimited by a tunnel (3) or a hood assembly sealed off from the surrounding atmosphere, the said tunnel or assembly being connected in a sealed manner to the said device or including the said device.
    6. Process according to Claim 5, characterized in that the said electric discharge, which has the said device as its seat and which is used to convert the said initial gaseous mixture, is created between a first electrode (14) and a second electrode (17), a layer (16) of a dielectric material being disposed on the surface of at least one of the electrodes (17) opposite the other electrode, and in that the said initial gaseous mixture traverses the discharge transversely to the electrodes.
    7. Process according to Claim 6, characterized in that the energy used in the said device, per unit area of dielectric, is greater than 1 W/cm2, preferably greater than 10 W/cm2.
    8. Process according to one of Claims 5 to 7, characterized in that the treatment atmosphere encountered successively by the component to be treated along the conveyor is divided into zones as follows:
      a) at least one of the devices (11, 4, 12) for the production of excited or unstable gaseous species converts a different initial gaseous mixture (7) from that converted by the device preceding it in the said tunnel (3) or assembly, and/or
      b) the adjacent gaseous mixture (9, 10) used at at least one of the devices (11, 4, 12) for the production of excited or unstable gaseous species is different from that used at the device preceding it in the said tunnel or assembly.
    9. Process according to Claim 8, characterized in that stages a) and b) take place at one single device.
    10. Use of an apparatus for the dry surface treatment of at least one metal surface portion for carrying out the process according to one of Claims 1 to 9, which apparatus comprises a tunnel (3) or hood assembly defining an inner space (31) traversed by conveying means (2) for the components (1) including the portion or portions to be treated, sealed off from the surrounding atmosphere, connected in a sealed manner to or including one or more devices (11, 4, 12) for the production of excited or unstable gaseous species arranged in series and/or in parallel, comprising at least one tubular gas passage (18) having an axis formed between an outer electrode (14) and an inner electrode (17), at least one of the electrodes including a dielectric coating (16) opposite the other electrode, the electrodes being connected to a high-voltage and high-frequency source, the outer electrode (14) surrounding the dielectric (16) and including an inlet (20) for the gas referred to as the initial gas and an outlet (21) for the gas referred to as the primary gas, this inlet and outlet being elongated, parallel to the axis and substantially diametrically opposite to one another, the said gas outlet opening into the interior of the said tunnel or assembly, the said tunnel or assembly being provided with at least one means (9, 10, 13) for the injection of a gas referred to as the adjacent gas which does not pass through the said device or devices.
    EP19940402726 1993-12-15 1994-11-29 Process and apparatus for the dry treatment of metallic surfaces Expired - Lifetime EP0658637B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    FR9315108A FR2713670B1 (en) 1993-12-15 1993-12-15 Method and device for treating metallic surfaces by dry process.
    FR9315108 1993-12-15

    Publications (2)

    Publication Number Publication Date
    EP0658637A1 EP0658637A1 (en) 1995-06-21
    EP0658637B1 true EP0658637B1 (en) 1999-10-20

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    EP (1) EP0658637B1 (en)
    JP (1) JP3421457B2 (en)
    DE (1) DE69421250T2 (en)
    ES (1) ES2139723T3 (en)
    FR (1) FR2713670B1 (en)

    Families Citing this family (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    FR2778190B1 (en) * 1998-05-04 2000-06-02 Air Liquide METHOD AND APPARATUS FOR TREATING METAL SURFACES BY DRY WAY

    Family Cites Families (5)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    SU1421249A1 (en) * 1985-10-30 1992-05-30 Предприятие П/Я А-1131 Method of cleaning article surface
    JP2811820B2 (en) * 1989-10-30 1998-10-15 株式会社ブリヂストン Continuous surface treatment method and apparatus for sheet material
    JP3206095B2 (en) * 1991-04-12 2001-09-04 株式会社ブリヂストン Surface treatment method and apparatus
    DE4113523A1 (en) * 1991-04-25 1992-10-29 Abb Patent Gmbh METHOD FOR TREATING SURFACES
    US5236512A (en) * 1991-08-14 1993-08-17 Thiokol Corporation Method and apparatus for cleaning surfaces with plasma

    Also Published As

    Publication number Publication date
    FR2713670B1 (en) 1996-01-12
    FR2713670A1 (en) 1995-06-16
    JP3421457B2 (en) 2003-06-30
    EP0658637A1 (en) 1995-06-21
    DE69421250T2 (en) 2000-05-31
    ES2139723T3 (en) 2000-02-16
    DE69421250D1 (en) 1999-11-25
    JPH0820859A (en) 1996-01-23

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