EP0990711B1 - Treatment of surfaces before thermally spray coating them - Google Patents

Treatment of surfaces before thermally spray coating them Download PDF

Info

Publication number
EP0990711B1
EP0990711B1 EP99117877A EP99117877A EP0990711B1 EP 0990711 B1 EP0990711 B1 EP 0990711B1 EP 99117877 A EP99117877 A EP 99117877A EP 99117877 A EP99117877 A EP 99117877A EP 0990711 B1 EP0990711 B1 EP 0990711B1
Authority
EP
European Patent Office
Prior art keywords
blasting
substrate surface
carbon dioxide
process according
solid state
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
EP99117877A
Other languages
German (de)
French (fr)
Other versions
EP0990711A1 (en
Inventor
Peter Dipl.-Ing. Heinrich
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.)
Linde GmbH
Original Assignee
Linde GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Linde GmbH filed Critical Linde GmbH
Publication of EP0990711A1 publication Critical patent/EP0990711A1/en
Application granted granted Critical
Publication of EP0990711B1 publication Critical patent/EP0990711B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles

Definitions

  • the invention relates to a method for processing a surface of a substrate in connection with the coating of the substrate surface with a spray layer by means of a thermal spray process, the substrate surface at a pretreatment before coating the substrate surface with the spray layer is roughened, and a device for processing a surface of a substrate in connection with the coating of the substrate surface a spray layer by means of a thermal spray process comprising means for Pretreatment of the substrate surface by roughening before coating the Substrate surface with the spray layer, the means for pretreatment a Blasting machine with accelerating means to accelerate the blasting medium on the Substrate surface included.
  • Thermal spraying includes processes in which spray additives are inside or melted, melted or melted outside of spray equipment and prepared Surfaces are hurled. The surfaces are not melted.
  • Thermal spraying for coating surfaces is known as a process variant autogenous flame spraying or high speed flame spraying, arc spraying, plasma spraying, detonation spraying and laser spraying.
  • thermal spraying is, for example, the European standard Can be found in EN 657.
  • Thermal spray processes are essentially characterized in that they enable evenly applied coatings.
  • Coatings can be applied by varying the spray materials can be adapted to different requirements.
  • the spray materials can be processed in the form of wires, rods or powder. With thermal In addition, thermal post-treatment can be provided for spraying.
  • the above-mentioned preparation of the surface to be coated Substrate prior to thermal spraying involves roughening the substrate surface.
  • this roughening is done by blasting before thermal Spraying with blasting media accomplished.
  • blasting agents are usually used Corundum or blasted gravel used.
  • By roughening the substrate surface "Activated". This becomes the stapling - the main mechanism of liability between Layer and substrate material - made possible.
  • Roughening can also be achieved by rough turning or rough grinding. However, a relatively high error rate occurs, which is why the rough turning or rough grinding is only used in borderline cases.
  • the invention is therefore based on the object of a method and a device of the type mentioned at the outset, which is a particularly favorable pretreatment of the substrate surface.
  • the ones listed above should be included Disadvantages are avoided or reduced as far as possible.
  • the abrasive should be disposed of be simplified and also versatile in use sensitive and critical substrates
  • This object is achieved for the method in that the pretreatment a blasting of the substrate surface to be coated by means of a Includes abrasive which contains one or more fluids hardened by cold contains a solid physical state.
  • the object is achieved for the device in that the Device means for blasting a blasting agent onto the substrate surface to be coated comprising one or more fluids hardened by cryogenic in contains solid state, and wherein the means for pretreating the Part of a system for coating the substrate surface with a spray layer by means of a thermal spray process.
  • the fluids solidified by means of cold can operate under normal conditions are in gaseous or liquid state.
  • the abrasives can, for example, from solidified carbon dioxide (dry ice) or consist of water ice.
  • dry ice solidified carbon dioxide
  • the speed and size of the blasting media can achieve the desired abrasiveness and be set.
  • the choice of Parameters depending on the material used for the abrasive based on its general Expertise, possibly also in connection with the implementation of appropriate obvious attempts.
  • the material of the Substrates influence the choice of parameters. It should be noted that the roughness for high-energy spraying processes such as high-speed flame spraying, plasma spraying or cold gas spraying does not have to be as high as in the low-energy spraying process.
  • the abrasive contains carbon dioxide in a solid state. Due to its physical properties, solidified carbon dioxide in particular offers significant advantages when used as an abrasive for the pretreatment of surfaces to be coated: carbon dioxide in a solid state (dry ice) has a temperature of around -78 ° C. When heated, carbon dioxide sublimes. When carbon dioxide is sublimated, an explosive increase in volume occurs by a factor of around 600, which effectively supports the treatment. Processing with carbon dioxide in a solid state is residue-free, since the sublimed gaseous carbon dioxide can escape without problems. Blasting agent preparation or blasting agent disposal is therefore not necessary. Solid carbon dioxide is advantageously used in the form of grated CO 2 blocks of grated ice and / or preferably CO 2 pellets.
  • the blasting is carried out in a fixed manner by means of blasting media Physical state immediately before coating by thermal spraying.
  • the abrasive fulfills a double function: on the one hand, it serves as Blasting media for the production of roughness and on the other hand as a coolant for the Cooling the substrate surface. It is even possible that the substrate surface cooled to a predetermined temperature by blasting with blasting media becomes.
  • the cooling of the substrate surface can be accomplished in that the desired cooling is achieved directly by blasting with solid carbon dioxide. But it is also possible that the cold of the sublimed gaseous carbon dioxide is used for further cooling.
  • the additional cooling by the sublimed gaseous carbon dioxide can thereby be increased that aids are coupled to the blasting system, which a Prevent the sublimated gaseous carbon dioxide from being drawn off quickly and an uncontrolled escape of the possibly still cold gaseous Prevent carbon dioxide.
  • aids can include a tunnel, contain a shaft, a rotary tube or the like.
  • the blasting according to the invention by means of blasting agents in a solid state of aggregation for roughening the substrate surface can take on a further function in addition to or instead of cooling: namely, the blasting can also have a roughening function. Clean the surface of the substrate. CO 2 pellets are particularly suitable here.
  • the spray layer is compacted again.
  • the quality of the spray layer can be markedly improved.
  • Abrasives are used.
  • steel balls are used for this.
  • Abrasives are used that contain one or more fluids hardened by cold contained in a solid state.
  • the blasting media for the Redensification of the substrate surface carbon dioxide in a solid state include.
  • the device for processing the substrate surface can in addition to the means for Blasting for pretreatment means for cooling, cleaning and / or post-compaction have the substrate surface.
  • the means of blasting for the Pretreatment can be different or preferably the same as the agents for blasting for the re-densification of the substrate surface.
  • the carbon dioxide has a solid state of matter an average size of 10 microns to 10 mm, preferably from 50 microns to 5 mm and particularly preferably from 1.5 mm to 2.5 mm.
  • the blasting systems work according to the pressure blasting or suction blasting method.
  • the blasting system can comprise a centrifugal wheel system, a pressure blasting system or an inline pelletizer.
  • a pressure jet system the solid CO 2 jet particles are generally metered into a gas stream from a storage container, conveyed with the gas stream to a jet nozzle and passed through the jet nozzle onto the castings to be treated.
  • the blasting nozzle is usually installed in a blasting gun.
  • jet nozzle is to be understood in a broader sense, so that this also includes, for example, an open tube.
  • CO 2 pellets are generated on site and accelerated onto the substrate surface to be treated.
  • the invention has the additional advantages of environmental friendliness and good Can be integrated into automated processes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)

Abstract

The surface of a substrate is pretreated with an abrasive containing one or more fluids solidified by cold in a solid aggregate state. Process for processing a surface of a substrate comprises roughening during pretreating the surface before coating it with a sprayed layer. An Independent claim is also included for an apparatus for carrying out the process.

Description

Die Erfindung betrifft ein Verfahren zur Bearbeitung einer Oberfläche eines Substrates im Zusammenhang mit dem Beschichten der Substratoberfläche mit einer Spritzschicht mittels eines thermischen Spritzverfahrens, wobei die Substratoberfläche bei einer Vorbehandlung vor dem Beschichten der Substratoberfläche mit der Spritzschicht aufgerauht wird, sowie eine Vorrichtung zur Bearbeitung einer Oberfläche eines Substrates im Zusammenhang mit dem Beschichten der Substratoberfläche mit einer Spritzschicht mittels eines thermischen Spritzverfahrens umfassend Mittel zur Vorbehandlung der Substratoberfläche durch Aufrauhen vor dem Beschichten der Substratoberfläche mit der Spritzschicht, wobei die Mittel zur Vorbehandlung eine Strahlanlage mit Beschleunigungsmitteln zur Beschleunigung der Strahlmittel auf die Substratoberfläche enthalten.The invention relates to a method for processing a surface of a substrate in connection with the coating of the substrate surface with a spray layer by means of a thermal spray process, the substrate surface at a pretreatment before coating the substrate surface with the spray layer is roughened, and a device for processing a surface of a substrate in connection with the coating of the substrate surface a spray layer by means of a thermal spray process comprising means for Pretreatment of the substrate surface by roughening before coating the Substrate surface with the spray layer, the means for pretreatment a Blasting machine with accelerating means to accelerate the blasting medium on the Substrate surface included.

Das thermische Spritzen umfaßt Verfahren, bei denen Spritzzusätze innerhalb oder außerhalb von Spritzgeräten an-, auf- oder abgeschmolzen und auf vorbereitete Oberflächen aufgeschleudert werden. Die Oberflächen werden dabei nicht aufgeschmolzen.Thermal spraying includes processes in which spray additives are inside or melted, melted or melted outside of spray equipment and prepared Surfaces are hurled. The surfaces are not melted.

Das thermische Spritzen zum Beschichten von Oberflächen kennt als Verfahrensvarianten das autogene Flammspritzen oder das Hochgeschwindigkeits-Flammspritzen, das Lichtbogenspritzen, das Plasmaspritzen, das Detonationsspritzen und das Laserspritzen.Thermal spraying for coating surfaces is known as a process variant autogenous flame spraying or high speed flame spraying, arc spraying, plasma spraying, detonation spraying and laser spraying.

Thermische Spritzverfahren sind in allgemeiner Form beispielsweise in

  • Übersicht und Einführung in das "Thermische Spritzen", Peter Heinrich, Linde-Berichte aus Technik und Wissenschaft, 52/1982, Seiten 29 bis 37.
oder
  • Thermisches Spritzen - Fakten und Stand der Technik, Peter Heinnch, Jahrbuch Oberflächentechnik 1992, Band 48, 1991, Seiten 304 bis 327. Metall-Verlag GmbH,
beschrieben.Thermal spray processes are in general form, for example in
  • Overview and introduction to "thermal spraying ", Peter Heinrich, Linde reports from technology and science, 52/1982, pages 29 to 37.
or
  • Thermal spraying - facts and state of the art, Peter Heinnch, Jahrbuch Oberflächentechnik 1992, volume 48, 1991, pages 304 to 327. Metall-Verlag GmbH,
described.

Weitere Details zum thermischen Spritzen sind beispielsweise der europäischen Norm EN 657 zu entnehmen.Further details on thermal spraying are, for example, the European standard Can be found in EN 657.

Thermische Spritzverfahren zeichnen sich im wesentlichen dadurch aus, daß sie gleichmäßig aufgetragene Beschichtungen ermöglichen. Durch thermische Spritzverfahren aufgetragene Beschichtungen können durch Variation der Spritzmaterialien an unterschiedliche Anforderungen angepaßt werden. Die Spritzmaterialien können dabei in Form von Drähten, Stäben oder als Pulver verarbeitet werden. Beim thermischen Spritzen kann zusätzlich eine thermische Nachbehandlung vorgesehen sein.Thermal spray processes are essentially characterized in that they enable evenly applied coatings. By thermal spraying Coatings can be applied by varying the spray materials can be adapted to different requirements. The spray materials can can be processed in the form of wires, rods or powder. With thermal In addition, thermal post-treatment can be provided for spraying.

In jüngerer Zeit wurde darüber hinaus ein weiteres thermisches Spritzverfahren entwickelt, welches auch als Kaltgasspritzen bezeichnet wird. Es handelt sich dabei um eine Art Weiterentwicklung des Hochgeschwindigkeits-Flammspritzens mit Pulver. Dieses Verfahren ist beispielsweise in der europäischen Patentschrift EP 0 484 533 B1 beschrieben. Beim Kaltgasspritzen kommt ein Zusatzwerkstoff in Pulverform zum Einsatz. Die Pulverpartikel werden beim Kaltgasspritzen jedoch nicht im Gasstrahl geschmolzen. Vielmehr liegt die Temperatur des Gasstrahles unterhalb des Schmelzpunktes der Zusatzwerkstoffpulverpartikel (EP 0 484 533 B1). Im Kaltgasspritzverfahren wird also ein im Vergleich zu den herkömmlichen Spritzverfahren "kaltes" bzw. ein vergleichsweise kälteres Gas verwendet. Gleichwohl wird das Gas aber ebenso wie in den herkömmlichen Verfahren erwärmt, aber in der Regel lediglich auf Temperaturen unterhalb des Schmelzpunktes der Pulverpartikel des Zusatzwerkstoffes.In addition, a further thermal spray process has recently been developed, which is also known as cold gas spraying. It is about a kind of further development of high-speed flame spraying with powder. This method is described, for example, in European patent EP 0 484 533 B1 described. A filler material in powder form is used for cold gas spraying Commitment. However, the powder particles are not melted in a gas jet during cold gas spraying. Rather, the temperature of the gas jet is below the melting point the filler material powder particle (EP 0 484 533 B1). In the cold gas spray process is a "cold" or "cold" used a comparatively colder gas. Nonetheless, the gas does the same as heated in the conventional methods, but usually only at temperatures below the melting point of the powder particles of the filler material.

Beim thermischen Spritzen kann insbesondere bei den hochenergetischen Spritzverfahren wie dem Hochgeschwindigkeits-Flammspritzen, dem Plasmaspritzen oder dem Kaltgasspritzen eine Kühlung erfolgen. Dazu kann beispielsweise Kohlendioxid, insbesondere in Form von CO2-Schnee, verwendet werden. Ein derartiges Verfahren ist beispielsweise aus der europäischen Patentschrift EP 0 546 359 B1

  • oder aus dem Firmenprospekt der LINDE AG, Werksgruppe Technische Gase, "LINSPRAY" - Thermisches Spritzen Dosiertes Kühlen mit CO2", Publikationsnummer 8542/1, Druckauflage 04/92,
oder
  • aus "Praktische Erfahrungen mit der Kühlung beim thermischen Spritzen", S. Werner, P. Heinrich, W. Schmidtke und R. Schüfer, DVS-Berichte Band 152, 1993, Seiten 45 bis 46,
bekannt.In the case of thermal spraying, cooling can take place in particular in the case of the high-energy spraying processes, such as high-speed flame spraying, plasma spraying or cold gas spraying. For example, carbon dioxide, in particular in the form of CO 2 snow, can be used for this purpose. Such a method is known, for example, from European patent EP 0 546 359 B1
  • or from the company brochure of LINDE AG, technical gases plant group, "LINSPRAY" - thermal spraying, dosed cooling with CO 2 ", publication number 8542/1, print edition 04/92,
or
  • from "Practical experience with cooling in thermal spraying", S. Werner, P. Heinrich, W. Schmidtke and R. Schüfer, DVS reports Volume 152, 1993, pages 45 to 46,
known.

Das oben angesprochene Vorbereiten der zu beschichtenden Oberfläche des Substrats vor dem thermischen Spritzen umfaßt eine Aufrauhen der Substratoberfläche. In der Regel wird dieses Aufrauhen durch Strahlen vor dem thermischen Spritzen mit Strahlmitteln bewerkstelligt. Als Strahlmittel werden dazu üblicherweise Korund oder Strahlkies eingesetzt. Durch das Aufrauhen wird die Substratoberfläche "aktiviert". Dadurch wird das Verklammern - der Haupthaftmechanismus zwischen Schicht und Substratwerkstoff - erst ermöglicht.The above-mentioned preparation of the surface to be coated Substrate prior to thermal spraying involves roughening the substrate surface. As a rule, this roughening is done by blasting before thermal Spraying with blasting media accomplished. For this purpose, blasting agents are usually used Corundum or blasted gravel used. By roughening the substrate surface "Activated". This becomes the stapling - the main mechanism of liability between Layer and substrate material - made possible.

Das Aufrauhen kann auch mittels Rauhdrehen oder Rauhschleifen erreicht werden. Dabei tritt allerdings eine relativ hohe Fehlerrate auf, weshalb auf das Rauhdrehen oder Rauhschleifen lediglich in Grenzfällen zurückgegriffen wird.Roughening can also be achieved by rough turning or rough grinding. However, a relatively high error rate occurs, which is why the rough turning or rough grinding is only used in borderline cases.

Aber auch beim Strahlen mit den bekannten Strahlmitteln wie Korund oder Strahlkies treten Nachteile auf. Diese Nachteile hängen in erster Linie damit zusammen, daß die genannten Strahlmittel zu Rückständen führen. Diese Rückstände erschweren und verteuern die Bearbeitung. Es besteht aber vor allem die Gefahr, daß durch Rückstände in der Grenzfläche zwischen Substratwerkstoff und Spritzschicht die Haftung vermindert wird. Die haftmindernde Wirkung der Rückstände führt insbesondere zu einer reduzierten Haftzugfestigkeit. Abgesehen davon kann das Strahlen mit Korund oder Strahlkies auch bei empfindlichen Substraten, beispielsweise aus der Medizinoder Luft- und Raumfahrttechnik, nur in beschränktem Maße eingesetzt werden.But also when blasting with the known blasting media such as corundum or blasting gravel there are disadvantages. These disadvantages are primarily related to the fact that abrasives mentioned lead to residues. These residues complicate and make processing more expensive. Above all, there is a risk of residues adhesion in the interface between substrate material and spray layer is reduced. In particular, the residue reduces the adhesion a reduced adhesive tensile strength. Apart from that, blasting with corundum or blasted gravel even with sensitive substrates, for example from medicine or Aerospace technology, can only be used to a limited extent.

Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren und eine Vorrichtung der eingangs genannten Art weiterzubilden, welche eine besonders günstige Vorbehandlung der Substratoberfläche mit sich bringt. Dabei sollten die oben aufgezählten Nachteile möglichst vermieden oder verringert werden. Insbesondere sollte die Strahlmittelentsorgung vereinfacht werden und eine vielseitige Einsetzbarkeit auch bei empfindlichen und kritischen Substraten ermöglicht werden The invention is therefore based on the object of a method and a device of the type mentioned at the outset, which is a particularly favorable pretreatment of the substrate surface. The ones listed above should be included Disadvantages are avoided or reduced as far as possible. In particular, the abrasive should be disposed of be simplified and also versatile in use sensitive and critical substrates

Diese Aufgabe wird erfindungsgemäß für das Verfahren dadurch gelöst, daß die Vorbehandlung ein Strahlen der zu beschichtenden Substratoberfläche mittels eines Strahlmittels umfaßt, welches ein oder mehrere mittels Kälte verfestigter Fluide in festem Aggregatzustand enthält.This object is achieved for the method in that the pretreatment a blasting of the substrate surface to be coated by means of a Includes abrasive which contains one or more fluids hardened by cold contains a solid physical state.

Die Aufgabe wird erfindungsgemäß für die Vorrichtung dadurch gelöst, daß die Vorrichtung Mittel zum Strahlen eines Strahlmittels auf die zu beschichtende Substratoberfläche umfaßt, welches ein oder mehrere mittels Kälte verfestigter Fluide in festem Aggregatzustand enthält, und wobei die Mittel zur Vorbehandlung der Substratoberfläche Teil einer Anlage zum Beschichten der Substratoberfläche mit einer Spritzschicht mittels eines thermischen Spritzverfahrens sind.The object is achieved for the device in that the Device means for blasting a blasting agent onto the substrate surface to be coated comprising one or more fluids hardened by cryogenic in contains solid state, and wherein the means for pretreating the Part of a system for coating the substrate surface with a spray layer by means of a thermal spray process.

Die aus mittels Kälte verfestigten Fluiden bestehenden können unter Normalbedingungen in gasförmigem oder flüssigem Aggregatzustand vorliegen. Die Strahlmittel können dabei beispielsweise aus verfestigtem Kohlendioxid (Trockeneis) oder auch aus Wassereis bestehen. Durch geeignete Wahl der Verfahrensparameter wie Geschwindigkeit und Größe der Strahlmittel kann die erwünschte Abrasivität erreicht und eingestellt werden. Für den einschlägigen Fachmann ergibt sich die Wahl der Parameter je nach verwendeten Material des Strahlmittels anhand seines allgemeinen Fachwissens, gegebenenfalls auch in Verbindung mit der Durchführung von entsprechenden naheliegenden Versuchen. Selbstverständlich hat auch das Material des Substrates auf die Parameterwahl Einfluß. Es ist zu beachten, daß die Rauhigkeit für hochenergetische Spritzverfahren wie dem Hochgeschwindigkeits-Flammspritzen, dem Plasmaspritzen oder dem Kaltgasspritzen nicht so hoch ausfallen muß wie bei den niederenergetischen Spritzverfahren.The fluids solidified by means of cold can operate under normal conditions are in gaseous or liquid state. The abrasives can, for example, from solidified carbon dioxide (dry ice) or consist of water ice. By a suitable choice of the process parameters such as The speed and size of the blasting media can achieve the desired abrasiveness and be set. For the relevant specialist, the choice of Parameters depending on the material used for the abrasive based on its general Expertise, possibly also in connection with the implementation of appropriate obvious attempts. Of course, the material of the Substrates influence the choice of parameters. It should be noted that the roughness for high-energy spraying processes such as high-speed flame spraying, plasma spraying or cold gas spraying does not have to be as high as in the low-energy spraying process.

Besondere Vorteile sind mit der Erfindung zu erzielen, wenn daß das Strahlmittel Kohlendioxid in festem Aggregatzustand enthält. Insbesondere verfestigtes Kohlendioxid bietet aufgrund seiner physikalischen Eigenschaften wesentliche Vorteile bei der Verwendung als Strahlmittel zur Vorbehandlung von zu beschichtenden Oberflächen: Kohlendioxid in festem Aggregatzustand (Trockeneis) besitzt eine Temperatur von etwa -78 °C. Bei Erwärmung sublimiert Kohlendioxid. Bei der Sublimation des Kohlendioxids tritt eine explosionsartige Volumenvergrößerung etwa um den Faktor 600 auf, was die Behandlung wirksam unterstützt. Die Bearbeitung mit Kohlendioxid in festem Aggregatzustand verläuft rückstandsfrei, da das sublimierte gasförmige Kohlen dioxiol problemlos entweichen kann. Eine Strahlmittelaufbereitung oder Strahlmittelentsorgung ist daher nicht erforderlich. Vorteilhaferweise wird festes Kohlendioxid in Form von CO2-Blockeisraspelkorn und/oder bevorzugt CO2-Pellets eingesetzt.Particular advantages can be achieved with the invention if the abrasive contains carbon dioxide in a solid state. Due to its physical properties, solidified carbon dioxide in particular offers significant advantages when used as an abrasive for the pretreatment of surfaces to be coated: carbon dioxide in a solid state (dry ice) has a temperature of around -78 ° C. When heated, carbon dioxide sublimes. When carbon dioxide is sublimated, an explosive increase in volume occurs by a factor of around 600, which effectively supports the treatment. Processing with carbon dioxide in a solid state is residue-free, since the sublimed gaseous carbon dioxide can escape without problems. Blasting agent preparation or blasting agent disposal is therefore not necessary. Solid carbon dioxide is advantageously used in the form of grated CO 2 blocks of grated ice and / or preferably CO 2 pellets.

In Ausgestaltung der Erfindung erfolgt das Strahlen mittels Strahlmitteln in festem Aggregatzustand unmittelbar vor dem Beschichten durch thermisches Spritzen.In one embodiment of the invention, the blasting is carried out in a fixed manner by means of blasting media Physical state immediately before coating by thermal spraying.

Das Strahlen mittels Strahlmitteln in festem Aggregatzustand aus unter Einwirkung von Kälte verfestigter Fluide unmittelbar vor dem Beschichten durch thermisches Spritzen kann neben der Vorbehandlung zur Herstellung einer aktivierten Oberfläche mit der erforderlichen Rauhigkeit auch eine Kühlung der Substratoberfläche bewirken. In diesem Fall erfüllt das Strahlmittel eine Doppelfunktion: Einerseits dient es als Strahlmittel für die Herstellung der Rauhigkeit und andererseits als Kühlmittel für die Kühlung der Substratoberfläche. Es ist sogar möglich, daß die Substratoberfläche durch das Strahlen mittels Strahlmitteln auf eine vorgegebene Temperatur abgekühlt wird.Blasting by means of blasting media in a solid state under action of fluids solidified at low temperatures immediately before coating by thermal In addition to pretreatment, spraying can be used to produce an activated surface with the required roughness also cause cooling of the substrate surface. In this case, the abrasive fulfills a double function: on the one hand, it serves as Blasting media for the production of roughness and on the other hand as a coolant for the Cooling the substrate surface. It is even possible that the substrate surface cooled to a predetermined temperature by blasting with blasting media becomes.

Die Kühlung der Substratoberfläche kann dadurch bewerkstelligt werden, daß die gewünschte Kühlung direkt durch das Strahlen mit festem Kohlendioxid erreicht wird. Es ist aber auch möglich, daß die Kälte des sublimierten gasförmigen Kohlendioxids zur weiteren Kühlung ausgenutzt wird.The cooling of the substrate surface can be accomplished in that the desired cooling is achieved directly by blasting with solid carbon dioxide. But it is also possible that the cold of the sublimed gaseous carbon dioxide is used for further cooling.

Die zusätzliche Kühlung durch das sublimierte gasförmige Kohlendioxid kann dadurch gesteigert werden, daß Hilfsmittel an die Strahlanlage angekoppelt sind, welche ein ungewollt rasches Abziehen des sublimierten gasförmigen Kohlendioxids verhindern und ein unkontrolliertes Entweichen des gegebenenfalls noch relativ kalten gasförmigen Kohlendioxids unterbinden. Diese Hilfsmittel können beispielsweise einen Tunnel, einen Schacht, ein Drehrohr oder dergleichen enthalten.The additional cooling by the sublimed gaseous carbon dioxide can thereby be increased that aids are coupled to the blasting system, which a Prevent the sublimated gaseous carbon dioxide from being drawn off quickly and an uncontrolled escape of the possibly still cold gaseous Prevent carbon dioxide. These aids can include a tunnel, contain a shaft, a rotary tube or the like.

Das erfindungsgemäße Strahlen mittels Strahlmitteln in festem Aggregatzustand zum Aufrauhen der Substratoberfläche kann neben oder anstatt der Kühlung eine weitere Funktion übernehmen: Das Strahlen kann nämlich außer dem Aufrauhen auch eine. Reinigung der Substratoberfläche bewirken. Hierbei eignen sich insbesondere CO2-Pellets.The blasting according to the invention by means of blasting agents in a solid state of aggregation for roughening the substrate surface can take on a further function in addition to or instead of cooling: namely, the blasting can also have a roughening function. Clean the surface of the substrate. CO 2 pellets are particularly suitable here.

In Weiterbildung der Erfindung kann nach dem Beschichten der Oberfläche des Substrates mit einer Spritzschicht mittels eines thermischen Spritzverfahrens durch Strahlen mittels Strahlmitteln ein Nachverdichten der Spritzschicht erfolgen. Auf diese Weise läßt sich die Qualität der Spritzschicht merklich verbessern. Als Strahlmittel für das Nachverdichten der Substratoberfläche können alle für diesen Zweck bekannten Strahlmittel eingesetzt werden. Beispielsweise werden dafür Stahlkugeln benutzt. Es können aber auch als Strahlmittel für das Nachverdichten der Substratoberfläche Strahlmittel verwendet werden, die ein oder mehrere mittels Kälte verfestigter Fluide in festem Aggregatzustand enthalten. Insbesondere können die Strahlmittel für das Nachverdichten der Substratoberfläche Kohlendioxid in festem Aggregatzustand umfassen.In a development of the invention, after coating the surface of the Substrate with a spray layer by means of a thermal spray process Blasting by means of blasting media, the spray layer is compacted again. To this In this way, the quality of the spray layer can be markedly improved. As an abrasive for the re-compacting of the substrate surface can all be known for this purpose Abrasives are used. For example, steel balls are used for this. It can also be used as an abrasive for the recompression of the substrate surface Abrasives are used that contain one or more fluids hardened by cold contained in a solid state. In particular, the blasting media for the Redensification of the substrate surface carbon dioxide in a solid state include.

Die Vorrichtung zur Bearbeitung der Substratoberfläche kann neben den Mitteln zum Strahlen für die Vorbehandlung Mittel zum Kühlen, zum Reinigen und/oder zum Nachverdichten der Substratoberfläche aufweisen. Die Mittel zum Strahlen für die Vorbehandlung können dabei unterschiedlich oder bevorzugt gleich zu den Mitteln zum Strahlen für das Nachverdichten der Substratoberfläche sein.The device for processing the substrate surface can in addition to the means for Blasting for pretreatment means for cooling, cleaning and / or post-compaction have the substrate surface. The means of blasting for the Pretreatment can be different or preferably the same as the agents for blasting for the re-densification of the substrate surface.

In Ausgestaltung der Erfindung weist das Kohlendioxid in festem Aggregatzustand eine mittlere Größe von 10 µm bis 10 mm, vorzugsweise von 50 µm bis 5 mm und besonders bevorzugt von 1,5 mm bis 2.5 mm auf.In an embodiment of the invention, the carbon dioxide has a solid state of matter an average size of 10 microns to 10 mm, preferably from 50 microns to 5 mm and particularly preferably from 1.5 mm to 2.5 mm.

Die Strahlanlagen insbesondere zum Strahlreinigen mit verfestigten Strahlmitteln wie beispielsweise mit CO2-Pellets arbeiten nach dem Druckstrahl- oder Saugstrahlverfahren. Die Strahlanlage kann eine Schleuderradanlage, eine Druckstrahlanlage oder einen Inline-Pelletierer umfassen. In einer Druckstrahlanlage werden die festen CO2-Strahlteilchen in der Regel aus einem Vorratsbehälter in einen Gasstrom eindosiert, mit dem Gasstrom zu einer Strahldüse gefördert und über die Strahldüse auf die zu behandelnden Gußteile geleitet. Die Strahldüse ist dabei in der Regel in einer Strahlpistole eingebaut. Der Begriff "Strahldüse" ist dabei in weiterem Sinne zu verstehen, so daß hiervon auch beispielsweise ein offenes Rohr umfaßt ist Bei einem Inline-Pelletierer werden CO2-Pellets vor Ort erzeugt und auf die zu behandelnden Substratoberfläche beschleunigt.The blasting systems, especially for blasting with solidified blasting media such as CO 2 pellets, work according to the pressure blasting or suction blasting method. The blasting system can comprise a centrifugal wheel system, a pressure blasting system or an inline pelletizer. In a pressure jet system, the solid CO 2 jet particles are generally metered into a gas stream from a storage container, conveyed with the gas stream to a jet nozzle and passed through the jet nozzle onto the castings to be treated. The blasting nozzle is usually installed in a blasting gun. The term “jet nozzle” is to be understood in a broader sense, so that this also includes, for example, an open tube. In an inline pelletizer, CO 2 pellets are generated on site and accelerated onto the substrate surface to be treated.

Die Erfindung birgt die zusätzlichen Vorteile der Umweltfreundlichkeit und der guten Integrierbarkeit in automatisierte Prozesse.The invention has the additional advantages of environmental friendliness and good Can be integrated into automated processes.

Claims (16)

  1. Process for treating a surface of a substrate in connection with the coating of the substrate surface with a sprayed layer by means of a thermal spraying process, the substrate surface being roughened in a pretreatment before the substrate surface is coated with the sprayed layer, characterized in that the pretreatment comprises blasting the substrate surface which is to be coated by means of a blasting agent which contains one or more fluids which have been solidified to the solid state of aggregation by means of refrigeration.
  2. Process according to Claim 1, characterized in that the blasting agent contains carbon dioxide in the solid state of aggregation.
  3. Process according to Claim 2, characterized in that solid carbon dioxide in the form of CO2 pellets and/or rasped grains from CO2 block ice is used.
  4. Process according to one of Claims 1 to 3, characterized in that the blasting by means of blasting agents in the solid state of aggregation takes place immediately before the coating by thermal spraying.
  5. Process according to one of Claims 1 to 4, characterized in that the substrate surface is cooled by the blasting by means of blasting agents in the solid state of aggregation.
  6. Process according to Claim 5, characterized in that the substrate surface is cooled to a predetermined temperature by the blasting by means of blasting agents.
  7. Process according to one of Claims 2 to 6, characterized in that sublimed gaseous carbon dioxide is used to cool the substrate surface.
  8. Process according to one of Claims 1 to 7, characterized in that the substrate surface is cleaned by the blasting by means of blasting agents in the solid state of aggregation.
  9. Process according to one of Claims 1 to 8, characterized in that after the surface of the substrate has been coated with a sprayed layer by means of a thermal spraying process, the sprayed layer is compacted further by means of blasting agents.
  10. Process according to Claim 9, characterized in that the blasting agent for further compression of the sprayed layer contains carbon dioxide in the solid state of aggregation, in particular CO2 pellets.
  11. Process according to one of Claims 2 to 10, characterized in that the solid carbon dioxide has a mean size of 10 µm to 10 mm, preferably of 50 µm to 5 mm, particularly preferably of 1.5 mm to 2.5 mm.
  12. Device for treating a surface of a substrate in connection with the coating of the substrate surface with a sprayed layer by means of a thermal spraying process, comprising means for pretreating the substrate surface by roughening prior to the coating of the substrate surface with the sprayed layer, the means for pretreating including a blasting installation with accelerating means for accelerating the blasting agents onto the substrate surface, characterized in that the device comprises means for blasting onto the substrate surface which is to be coated a blasting agent which contains one or more fluids which have been solidified to the solid state of aggregation by means of refrigeration, the means for pretreating the substrate surface being part of an installation for coating the substrate surface with a sprayed layer by means of a thermal spraying process.
  13. Device according to claim 12, characterized in that the device includes means for blasting carbon dioxide in the solid state of aggregation as the blasting agent.
  14. Device according to one of Claims 12 or 13, characterized in that the device includes means for cooling, cleaning and/or further compressing the substrate surface.
  15. Device according to one of Claims 12 to 14, characterized in that the blasting installation comprises a centrifugal wheel installation, a pressure jet installation or an in-line pelletizer.
  16. Device according to one of Claims 13 to 15, characterized in that auxiliary means for preventing undesirably rapid extraction of the sublimed gaseous carbon dioxide are coupled to the blasting installation.
EP99117877A 1998-09-29 1999-09-10 Treatment of surfaces before thermally spray coating them Expired - Lifetime EP0990711B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19844668A DE19844668A1 (en) 1998-09-29 1998-09-29 Processing of surfaces to be coated by means of thermal spraying
DE19844668 1998-09-29

Publications (2)

Publication Number Publication Date
EP0990711A1 EP0990711A1 (en) 2000-04-05
EP0990711B1 true EP0990711B1 (en) 2003-07-09

Family

ID=7882667

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99117877A Expired - Lifetime EP0990711B1 (en) 1998-09-29 1999-09-10 Treatment of surfaces before thermally spray coating them

Country Status (4)

Country Link
EP (1) EP0990711B1 (en)
AT (1) ATE244775T1 (en)
DE (2) DE19844668A1 (en)
PL (1) PL335533A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004056179A1 (en) * 2004-11-20 2006-05-24 Borgwarner Inc. Powertrain Technical Center, Auburn Hills Method for producing a compressor housing
EP1898003A1 (en) * 2006-09-05 2008-03-12 SBZ Schörling-Brock Zweiwegetechnik GmbH Method for removing dirt, preferably from walls and grounds of tunnels, in a fast and secure way
DE102006045666A1 (en) * 2006-09-27 2008-04-03 Mtu Aero Engines Gmbh Process for the production of surface coatings on components
FR2912072A1 (en) * 2007-02-05 2008-08-08 Hmrexpert Soc Par Actions Simp Coating deposit cooling and cleaning method for substrate, involves carrying out coating deposit by projecting pellet jet on deposit layer to cool substrate and coating deposit and to clean impurities on surface of layer in partial manner
DE102013107400B4 (en) 2013-07-12 2017-08-10 Ks Huayu Alutech Gmbh Method for removing the overspray of a thermal spray burner
DE102022106559A1 (en) 2022-03-21 2023-09-21 Muyo Oberflächentechnik GmbH METHOD AND DEVICE FOR PRETREATING A COMPONENT BEFORE A COATING PROCESS

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58165962A (en) * 1982-03-24 1983-10-01 Ishikawajima Harima Heavy Ind Co Ltd Ice grain blast method
DE3738246A1 (en) * 1987-11-11 1989-05-24 Werner & Zeisse Gmbh & Co METHOD AND DEVICE FOR REMOVING COATINGS AND IMPURITIES
JPH0646451B2 (en) * 1987-12-11 1994-06-15 大陽酸素株式会社 Magnetic disk substrate processing method
FR2627121B1 (en) * 1988-02-12 1994-07-01 Carboxyque Francaise METHOD, INSTALLATION AND SPRAY NOZZLE FOR THE TREATMENT OF TRAPS BY BLASTING BLAST
JPH0250947A (en) * 1988-08-11 1990-02-20 Yamada Kinzoku Boshoku Kk Sealing treatment for sprayed deposit
DE3844290C1 (en) * 1988-12-30 1989-12-21 Uranit Gmbh, 5170 Juelich, De
CA2097222A1 (en) * 1992-06-01 1993-12-02 Somyong Visaisouk Particle blasting utilizing crystalline ice
WO1997020961A1 (en) * 1995-12-06 1997-06-12 Black Ice Golf Company, L.L.C. Method for coating a golf club striking surface
DE19636305C1 (en) * 1996-09-06 1998-03-12 Linde Ag Method for removal of coatings or linings from surfaces
DE19639437A1 (en) * 1996-09-25 1998-04-02 Siemens Ag Cleaning or roughening metal surface especially relay contact
DE19781876D2 (en) * 1997-06-20 1999-09-09 Gevi Process for the rehabilitation of pipelines using dry ice

Also Published As

Publication number Publication date
EP0990711A1 (en) 2000-04-05
PL335533A1 (en) 2000-04-10
DE19844668A1 (en) 2000-03-30
ATE244775T1 (en) 2003-07-15
DE59906246D1 (en) 2003-08-14

Similar Documents

Publication Publication Date Title
EP1382720B1 (en) Cold gas spraying method and device
EP0911425A1 (en) Method for thermally coating surfaces
DE102010017859B4 (en) Method for processing a surface of a component
EP0061756A1 (en) Apparatus for the surface-treatment of buildings and ships
EP2737101A2 (en) Coating method using special powdered coating materials and use of such coating materials
EP0316264B1 (en) Method and device for stripping enamel and for removing layers from surfaces
CN113275524B (en) Apparatus and method for producing strip by rapid solidification technology and metal strip
EP0990711B1 (en) Treatment of surfaces before thermally spray coating them
DE102006002653A1 (en) Dry ice-water-mixture blasting method involves adding blasting water containing dry ice particles in mixing ratio which is changeable/constant during blasting procedure, where addition of water takes place under usage of injector principle
DE3224305A1 (en) METHOD FOR PRODUCING A TENSION-FREE SENSITIVE CERAMIC THERMAL BARRIER LAYER ON A METAL SUBSTRATE
DE102013107400B4 (en) Method for removing the overspray of a thermal spray burner
EP1034890A2 (en) Method and device for blasting with different types of blasting medium
EP0924315B1 (en) Production of hot gas for thermal spraying
EP3325215A1 (en) Method for treating surfaces by means of a blasting medium consisting of dry ice particles
EP2014415A1 (en) Method for treatment of a surface of a gas turbine engine component
DE19756506C2 (en) Process for abrasive water jet cutting
DE4041307A1 (en) METHOD FOR DE-PAINTING WORKPIECES
EP3822023B1 (en) Device for dry ice treatment of surfaces and method for treating surfaces
DE102011086496A1 (en) Radiating unit or radiating device for producing water ice for removing tough dirt layers, oil and blasting film or corrosion from workpiece, is provided with phosphating agent that is added to water for producing water ice
DE102020104312A1 (en) Plant and method for producing a strip with a rapid solidification technology and metallic strip
DE102020104311A1 (en) Plant and method for producing a strip with a rapid solidification technology and metallic strip
DE19636304A1 (en) Method for finishing paint=covered wooden surfaces
EP3984697A1 (en) Device and method for cleaning surfaces using co2 particles
CH704074B1 (en) A process for the production of coatings from fine powders.
DE102013226690A1 (en) Device, useful for thermally coating surface of cylinder walls of internal combustion engine, comprises housing, cathode, anode, and insulating element, where housing has e.g. thick chromium coating as non-releasable non-stick surface

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: LINDE TECHNISCHE GASE GMBH

17P Request for examination filed

Effective date: 20001004

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: LINDE GAS AG

AKX Designation fees paid

Free format text: AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: LINDE AG

17Q First examination report despatched

Effective date: 20020625

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030709

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20030709

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030709

Ref country code: GB

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030709

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030709

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030709

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59906246

Country of ref document: DE

Date of ref document: 20030814

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030910

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030910

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030910

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030930

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030930

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20031009

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20031009

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20031009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20031020

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20031209

GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

Effective date: 20030709

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

BERE Be: lapsed

Owner name: *LINDE A.G.

Effective date: 20030930

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20040414

EN Fr: translation not filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20080926

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100401