EP0658637B1 - Verfahren und Vorrichtung zur Trockenbehandlung von metallischen Oberflächen - Google Patents

Verfahren und Vorrichtung zur Trockenbehandlung von metallischen Oberflächen 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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EP
European Patent Office
Prior art keywords
gas
tunnel
process according
gaseous mixture
excited
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.)
Expired - Lifetime
Application number
EP19940402726
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English (en)
French (fr)
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EP0658637A1 (de
Inventor
Thierry Sindzingre
Stéphane 14 Rés. du Parc du Château Rabia
Daniel Rés. du Val Fleuri Guerin
Christian Larquet
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.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Publication of EP0658637A1 publication Critical patent/EP0658637A1/de
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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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • ing And Chemical Polishing (AREA)

Claims (10)

  1. Verfahren zur trockenen Oberflächenbehandlung mindestens eines Teils einer metallischen Oberfläche zur Durchführung einer oder mehrerer der folgenden Aufgaben auf dieser metallischen Oberfläche: Reinigung, Entfettung, Oberflächenaktivierung,
       dadurch gekennzeichnet, daß man den Teil bei einem Druck in der Nähe des Normaldrucks mit einer Gasatmosphäre behandelt, die angeregte oder instabile und im wesentlichen von elektrisch geladenen Spezies freie Spezies enthält, die man
    aus einem am Gasausgang (6) mindestens einer Vorrichtung (4) zur Bildung angeregter oder instabiler Gasspezies, in der ein Ausgangsgasgemisch (7) aus einem inerten und/oder Reduktions- und/oder Oxidationsgas durch elektrische Entladung umgewandelt wird, erhaltenen Primärgasgemisch (8) und
    einem begleitenden Gasgemisch (9, 10), das die Vorrichtung (4) nicht durchströmt hat, erhält.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das begleitende Gasgemisch reduzierend ist.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das begleitende Gasgemisch Silan SiH4 enthält.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das den zu behandelnden metallischen Teil enthaltende Werkstück auf eine Temperatur von höchstens 600°C gebracht wird.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das den zu behandelnden metallischen Teil enthaltende Werkstück (1) mittels eines Fördersystems (2), das einen von einem Tunnel (3) oder einer von der umgebenden Atmosphäre isolierten Verkleidungsbaugruppe begrenzten Innenraum (31) durchläuft, gegenüber dem Gasausgang (6) der Vorrichtung (4), gegebenenfalls gegenüber den Gasausgängen mehrerer parallel über die Breite des Werkstücks und/oder nacheinander gegenüber den Gasausgängen mehrerer in Serie angeordneter Vorrichtungen (11, 4, 12) gebracht wird, wobei der Tunnel oder die Baugruppe dicht mit der Vorrichtung verbunden ist oder diese einschließt.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die zur Umwandlung des Ausgangsgasgemischs verwendete elektrische Entladung, die in der Vorrichtung erfolgt, zwischen einer ersten Elektrode (14) und einer zweiten Elektrode (17) erzeugt wird, wobei eine Schicht (16) aus einem dielektrischen Material auf der Oberfläche mindestens einer der Elektroden (17) gegenüber der anderen Elektrode angeordnet ist, und daß das Ausgangsgasgemisch die Entladung quer zu den Elektroden durchläuft.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß die in der Vorrichtung eingesetzte Energie, bezogen auf die Flächeneinheit des Dielektrikums, größer als 1 W/cm2 und vorzugsweise größer als 10 W/cm2 ist.
  8. Verfahren nach einem der Ansprüche 5 bis 7, dadurch gekennzeichnet, daß die Behandlungsatmosphäre, in welche das zu behandelnde Werkstück nacheinander eintritt, entlang dem Förderer folgendermaßen in Zonen eingeteilt ist:
    a) in mindestens einer der Vorrichtungen (11, 4, 12) zur Bildung angeregter oder instabiler Gasspezies wird ein Ausgangsgasgemisch (7), das sich von dem in der vorhergehenden Vorrichtung in dem Tunnel (3) oder der Baugruppe ungewandelten Ausgangsgasgemisch unterscheidet, umgewandelt und/oder
    b) das in mindestens einer der Vorrichtungen (11, 4, 12) zur Bildung angeregter oder instabiler Gasspezies eingesetzte begleitende Gasgemisch (9, 10) unterscheidet sich von dem in der in dem Tunnel oder der Baugruppe vorangehenden Vorrichtungeingesetzten begleitenden Gasgemisch.
  9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß die Stufen a) und b) in derselben Vorrichtung ablaufen.
  10. Verwendung einer Vorrichtung zur trockenen Oberflächenbehandlung mindestens eines Teils einer metallischen Oberfläche zur Durchführung des Verfahrens nach einem der Ansprüche 1 bis 9, enthaltend einen Tunnel (3) oder eine Verkleidungsbaugruppe, der bzw. die einen Innenraum (31) begrenzt, der von Fördermitteln (2) für die Werkstücke (1) mit dem oder den zu behandelnden Teilen durchlaufen wird, von der umgebenden Atmosphäre isoliert ist und dicht mit einer oder mehreren, in Serie und/oder parallel angeordneten Vorrichtungen (11, 4, 12) zur Bildung angeregter oder instabiler Gasspezies verbunden ist oder diese einschließt, und mindestens einen rohrförmigen Gasdurchlaß (18) mit einer zwischen einer Außenelektrode (14) und einer Innenelektrode (17) gebildeten Achse, wobei mindestens eine der Elektroden gegenüber der anderen eine dielektrische Beschichtung (16) trägt, die Elektroden mit einer Hochspannungs- und Hochfrequenzquelle verbunden sind, die Außenelektrode (14) das Dielektrikum (16) umgibt und einen länglichen Eingang (20) für das sogenannte Ausgangsgas und einen länglichen Ausgang (21) für das sogenannte Primärgas umfaßt, die parallel zur Achse und weitgehend diametral gegenüberliegend angeordnet sind, wobei der Gasausgang in das Innere des Tunnels oder der Baugruppe mündet, wobei der Tunnel oder die Baugruppe mit mindestens einem Einblasmittel (9, 10, 13) für ein sogenanntes Begleitgas versehen ist, das die Vorrichtung(en) nicht durchläuft.
EP19940402726 1993-12-15 1994-11-29 Verfahren und Vorrichtung zur Trockenbehandlung von metallischen Oberflächen Expired - Lifetime EP0658637B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9315108 1993-12-15
FR9315108A FR2713670B1 (fr) 1993-12-15 1993-12-15 Procédé et dispositif de traitement de surfaces métalliques par voie sèche.

Publications (2)

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

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EP19940402726 Expired - Lifetime EP0658637B1 (de) 1993-12-15 1994-11-29 Verfahren und Vorrichtung zur Trockenbehandlung von metallischen Oberflächen

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

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2778190B1 (fr) * 1998-05-04 2000-06-02 Air Liquide Procede et appareil de traitement de surfaces metalliques par voie seche

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1421249A1 (ru) * 1985-10-30 1992-05-30 Предприятие П/Я А-1131 Способ очистки поверхности изделий
JP2811820B2 (ja) * 1989-10-30 1998-10-15 株式会社ブリヂストン シート状物の連続表面処理方法及び装置
JP3206095B2 (ja) * 1991-04-12 2001-09-04 株式会社ブリヂストン 表面処理方法及びその装置
DE4113523A1 (de) * 1991-04-25 1992-10-29 Abb Patent Gmbh Verfahren zur behandlung von oberflaechen
US5236512A (en) * 1991-08-14 1993-08-17 Thiokol Corporation Method and apparatus for cleaning surfaces with plasma

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

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