EP1027169B1 - Method for corrosion-resistant coating of metal substrates by means of plasma polymerisation - Google Patents

Method for corrosion-resistant coating of metal substrates by means of plasma polymerisation Download PDF

Info

Publication number
EP1027169B1
EP1027169B1 EP19980961076 EP98961076A EP1027169B1 EP 1027169 B1 EP1027169 B1 EP 1027169B1 EP 19980961076 EP19980961076 EP 19980961076 EP 98961076 A EP98961076 A EP 98961076A EP 1027169 B1 EP1027169 B1 EP 1027169B1
Authority
EP
European Patent Office
Prior art keywords
plasma
corrosion
metal substrate
treatment
coating
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
EP19980961076
Other languages
German (de)
French (fr)
Other versions
EP1027169A2 (en
Inventor
Wolfgang Semrau
Alfred Baalmann
Henning Stuke
Klaus-Dieter Vissing
Hartmut Hufenbach
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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 Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP1027169A2 publication Critical patent/EP1027169A2/en
Application granted granted Critical
Publication of EP1027169B1 publication Critical patent/EP1027169B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00Processes for applying liquids or other fluent materials
    • B05D1/62Plasma-deposition of organic layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141Plasma treatment
    • B05D3/142Pretreatment
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31678Of metal

Definitions

  • the invention relates to a method for the corrosion-resistant coating of Metal substrates using plasma polymerization.
  • the procedure is particular suitable for corrosion-proof aluminum and aluminum alloys coat.
  • plasma polymerization is a process by which Exposure of a plasma to an organic molecule in the gas phase Solid coatings with predominantly organic character and excellent properties.
  • Plasma polymerization belongs to the group of low pressure plasma processes and is growing used industrially. The great interest in this technology is due to the Advantages of a fast, contactless, dry chemical as well as that Part of the coating process that is not very stressful to the workpiece.
  • Finned tubes made of AlMgSi0.5 are often used in condensing boilers related. Such finned tubes show under extreme conditions and not in limits with regard to the approved gas composition always sufficient corrosion resistance.
  • Paint systems are also not an alternative. Paints as Surface protection leads to an impairment of the heat conduction, which in the the present case can only be tolerated within a narrow limit. Furthermore, leads conventional lacquer coatings to water vapor diffusion Infiltration of the protective layer. During the subsequent condensation of the metal surface this causes the layer to lift off and one Accelerate the corrosion process, like this from localized Types of corrosion is known.
  • DE-A-42 16 999 describes a process for the surface coating of Silver objects known, in which the surface first with a removing plasma and then treating the surface with a Plasma polymer is coated, initially with a coupling layer, then a permeation-preventing surface layer and finally one Sealing layer are generated.
  • the coupling layer especially ethylene and vinyltrimethylsilane are used for which permeation-preventing layer of ethylene and for sealing Hexamethyldisiloxane in combination with oxygen as plasma-forming Monomers, with a continuous transition between the plasma-forming Monomers takes place.
  • the coatings are largely scratch-resistant and form a good tarnish protection, but can be set so that with a cleaning agent can be removed.
  • a coating of Aluminum substrates do not lead to corrosion-resistant coatings.
  • This goal is achieved with a method of the type mentioned in the introduction, in which the substrate is subjected to mechanical, chemical and / or electrochemical smoothing in a pretreatment step and then at a temperature of less than 200 ° C. and a pressure of 10 -5 to 100 mbar is exposed to a plasma, in a first step activating the surface in a reducing plasma and in a second step the plasma polymer from a plasma which at least optionally contains an oxygen, nitrogen or sulfur which can be evaporated under the conditions of the plasma organosilicon compound, which may contain fluorine atoms, is deposited.
  • the plasma treatment again consists of 2 Steps, firstly from a treatment of the surface with a reducing plasma, which removes the surface, and a second step in which the actual coating is applied directly to the plasma-pretreated metal layer is applied.
  • the pretreatment, especially smoothing the surface of the metal substrate can be done with mechanical, chemical or electrochemical means. Combinations of mechanical and chemical are particularly preferred Smoothing.
  • the mechanical and / or chemical smoothing can in any case electrochemical smoothing can be added if the respective Metal substrate allows this.
  • the electropolishing process is, for example, at Finned tubes not available for physical / technical reasons Suitable for surface treatment. Here you are on chemical processes like acidic or alkaline pickling. According to DE-C-40 39 479 can also a combination of pickling in connection with a mechanical malfunction of the Surface by wiping, brushing, blasting or the like come, in particular the workpiece with a liquid jet that contains the mordant and abrasive particles.
  • the pickling process used to smooth the surface is to chemical processes involving aggressive chemicals mainly oxide, rust and scale layers of the respective Metal surface to be removed.
  • Pickling liquids are mostly Acids that attack both the surface layers and the metal itself.
  • the Pickling is not a uniform process. Rather, different chemical processes run and physical processes side by side and also one after the other.
  • the Processes are often electrochemical in nature, being between the metal oxides and the metal surface to form local elements.
  • Electropolishing is a process used to shine metal surfaces the ridges and ridges are removed electrolytically.
  • stains including glossy stains
  • mechanical surface treatment processes further uniform and accelerate.
  • such a combination comes in particular of mechanical and chemical surface treatment processes for Smoothing, as described in DE-C-40 39 479, is used.
  • the surface is covered by the smoothing treatment an average roughness of less than 350 nm, preferably less than 250 nm smoothed.
  • average roughness of less than 100 nm can be achieved.
  • the smoothed surfaces achieved in this way are still not optimally suited for the application of a plasma polymer.
  • a plasma polymer Will follow the mechanical / chemical and / or electrochemical Smoothing a plasma polymer applied, this does not show the desired service life under corrosive conditions.
  • a further surface treatment using a reductively set Plasma especially a hydrogen plasma.
  • This plasma treatment takes place at temperatures of ⁇ 200 ° C at pressures of ⁇ 100 mbar, in particular at ⁇ 100 ° C and ⁇ 10 mbar.
  • the hydrogen as a carrier of the plasma can other gases are added, for example hydrocarbons and in particular olefins, as described below, and oxygen, nitrogen or also argon, taking care that the reducing character is maintained.
  • a plasma polymer put down.
  • the main component of this plasma polymer is hydrocarbon and / or organosilicon compound, the oxygen, nitrogen or sulfur atoms May contain, these hydrocarbon or organosilicon Compound has a boiling point, which it under the in the Plasma coating chamber prevailing temperature and Pressure conditions is evaporable.
  • alkanes come for this, Alkenes, aromatic hydrocarbons, silanes, siloxanes, silazanes and silathiane in question, preferably siloxanes.
  • the use of is particularly preferred Hexamethyldisiloxane and hexamethylcyclotrisiloxane.
  • co-monomer for the formation of the plasma polymer from organosilicon Monomers are hydrocarbons, especially olefins, for example ethylene, propene and cyclohexene.
  • Silanes, in particular Vinyl-containing organosilicon compounds can also be used as co-monomers are used, for example vinyltrimethylsilazane.
  • This unsaturated monomers can contain O, N or S atoms
  • Organosilicon compound in fixed or changing proportions be admixed, a graded admixture being considered. For example, with a step-by-step build-up of the plasma polymer a transition layer can be built up on the metal surface exclusively or predominantly from the organosilicon compound exists, and then the hydrocarbon is added. The reverse procedure is also possible. That way The properties of the plasma polymer coating can be change that optimal attachment to the metal substrate and / or optimal resistance to corrosive substances is given.
  • Graded structure is known for example from DE-A-42 16 999.
  • plasma polymerization can include other Gases are fed, for example oxygen, nitrogen or argon, around the To influence properties of the plasma and the plasma polymer.
  • Plasma polymerization generally takes place at a temperature of ⁇ 200 ° C, preferably ⁇ 100 ° C and in particular about 60 ° C instead.
  • the pressure in the Plasma coating chamber is generally ⁇ 10 mbar.
  • the layer formed by the plasma polymer formation on the metal substrate suitably has a thickness of 100 nm to 10 microns. But it is without further possible to use layer thicknesses of less than 100 nm for special purposes produce.
  • Plasma polymer coatings is a smoothing of the Surface achieved by a leveling dressing, the effect of which by a superimposed light mechanical component is increased and evened out. There is therefore less mechanical clamping of the Polymer coating on the metal substrate due to a relatively high Roughness of the substrate, but rather a more chemical one Connection to free valences of the exposed and etched metal surface. It is generally an almost mirror-bright, visually appealing Surface reached on unstructured metal surfaces. In particular is achieved that the thickness of the coating no longer in the Surface structures of a rough metal surface "go down", but one uniform, even layer is created.
  • a further increase in long-term corrosion resistance is achieved by the Installation of a corrosion inhibitor which can be evaporated in vacuo, preferably achieved the lowest layer of the plasma polymer coating.
  • a corrosion inhibitor which can be evaporated in vacuo, preferably achieved the lowest layer of the plasma polymer coating.
  • Corrosion inhibitor is applied directly to the substrate surface, ie is not directly in the liability level and weakens it.
  • Much more a long-distance effect is achieved, especially with the use of conductive Polymers is connected.
  • Suitable such polymers are, for example Polyanilines that have a low vapor pressure in vacuum or in finely divided form can be introduced into the plasma polymer, in one Amount from 0.1 to 1% by weight.
  • the method according to the invention can also be used to: applying plasma polymeric primer to a metal substrate, which then is then supplemented by further coatings.
  • This can corrosion-resistant coatings for various purposes with high Coating thickness can be achieved, the enough layer thickness for an abrasive Have stress. Ormocere are particularly well suited for this. Ormoceren coatings have a structural structure Similarity to highly cross-linked plasma polymer coatings, can but built up in vacuum without the relatively slow coating process become. The typical layer thicknesses are of the order of 1 up to 100 nm. The combination offers similarly good corrosion properties as with plasma polymer coatings alone.
  • Rectangular samples made of AlMgSi0.5 were used as test material related.
  • the samples were initially a multi-stage Subject to cleaning procedures to remove foreign matter such as oils and fats remove. Then the surface of the sheets was cleaned with a combined pickling and electropolishing processes.
  • the metal samples are then pickled in a pickle consisting of 46.0 parts of water, 50.0 parts of concentrated nitric acid and 4.0 parts of hydrofluoric acid at room temperature for 120 s. After rinsing with water and ethanol, the workpiece was then polished electrochemically. A mixture of 78 ml of 70 to 72% chloric acid, 120 ml of distilled water, 700 ml of ethanol and 100 ml of butyl glycol was used as the electrolyte. The electropolishing was carried out over a period of 180 s at an electrolyte temperature of -15 to + 8 ° C, a polishing current of 5 to 18 A / dm 2 and a polishing voltage of 19 to 11 V.
  • the sample was rinsed off with water and in the ultrasonic bath 10 min. treated in cold water. In the end dried with hot air.
  • the workpiece had a matt surface an average roughness of 0.570 ⁇ m (averaged over 5 measurements). After The electropolishing roughness was less than 100 nm. The surface was shiny.
  • the plasma treatment was carried out in a conventional plasma polymerization plant performed, in which the monomer gas is introduced into the vacuum tank and by high frequency alternating current and / or microwave energy for Plasma formation was stimulated.
  • the aluminum workpiece at 60 ° C and 50 mbar for 120 s with a hydrogen plasma.
  • the Hydrogen was gradually added by feeding in hexamethyldisiloxane a pressure of 10 mbar.
  • the volume flow was 500 ml / min Output was max. 5 KW.
  • the application took place in a layer thickness of 500 nm.
  • the example was varied in that the plasma polymerization first on the metal surface as a plasma polymer made of ethylene Monomer was applied in increasing amounts Hexamethyldisiloxane was added until the ethylene was completely displaced was.
  • the monomers were oxygen and Nitrogen added.
  • the Plasma polymer layer has a good connection to the metal surface.
  • the Plasma polymer layer is amorphous and practically free of defects, i. H. she has none Pores or inclusions.
  • the aluminum sheets coated according to the invention proved to be at 350 ° C under conditions such as those in a heat exchanger for condensing boilers rule, absolutely constant. They also show a degraded Surface tension, which is why there is a lower tendency to mineral Deposits, for example in the form of scale, exist. The reduced surface tension also protects against biological growth, for example, for workpieces that are exposed to sea water,

Abstract

The invention relates to a method for corrosion-resistant coating of metal substrates by means of plasma polymerization, wherein the substrate is subjected to mechanical, chemical and/or electrochemical smoothing in a pre-treatment step and is subsequently exposed to a plasma at a temperature of less than 200° C. and at a pressure of 10-5 bis 100 mbars, whereby in a first step the surface is activated in a reducing plasma and in a second step the polymer is separated from a plasma containing at least one hydrocarbon or silico-organic compound which can be vaporized in plasma conditions, optionally contains oxygen, nitrogen or sulphur and can contain fluorine.

Description

Die Erfindung betrifft ein Verfahren zur korrosionsfesten Beschichtung von Metallsubstraten mittels Plasmapolymerisation. Das Verfahren ist insbesondere dazu geeignet, Aluminium und Aluminiumlegierungen korrisionsfest zu beschichten.The invention relates to a method for the corrosion-resistant coating of Metal substrates using plasma polymerization. The procedure is particular suitable for corrosion-proof aluminum and aluminum alloys coat.

Seit die Forschung sich mit der Erzeugung plasmapolymerer Schichten durch Polymerisationsprozesse, die durch Zugabe gasförmiger Monomere in einen Gasentladungsprozess, der die notwendige Energie für die Polymerisation liefert, beschäftigt, hat es an Versuchen nicht gefehlt, diese Schichten so abzuscheiden, daß sie die beschichtete Oberfläche vor unterschiedlichen Angriffsarten zu schützen imstande sind. Diese Funktion ist keineswegs trivial, handelt es sich doch bei den plasmapolymeren Schichten um ausgesprochene Dünnschichten, die im Nanometerbereich bis hin zu wenigen Mikrometern anzusiedeln sind. Neben der Entwicklung von Kratzfestschichten, z. B. für optische Funktionselemente aus Kunststoffen (WO-A-8504601) wurde auch versucht, metallische Werkstoffe durch diese Art von Schichten zu schützen, mit mäßigem Erfolg. Selbst Angriffe, die als korrosiv nicht gravierend angesehen werden müssen, widerstanden diese Schichten nur für sehr kurze Zeiten.Since research has been dealing with the production of plasma polymer layers Polymerization processes by adding gaseous monomers in one Gas discharge process, which provides the necessary energy for the polymerization, busy, there was no lack of attempts to deposit these layers in such a way that they cover the coated surface from different types of attack are able to protect. This function is by no means trivial, it is but in the case of plasma polymer layers, there are pronounced thin layers that in the nanometer range down to a few micrometers. Next the development of scratch-resistant layers, e.g. B. for optical functional elements made of plastics (WO-A-8504601) has also been tried, metallic materials to protect by this type of layers, with moderate success. Even attacks, which must not be considered as corrosive, resisted them Shifts only for very short times.

In allen bisher bekannt gewordenen Versuchen auf Aluminiumwerkstoffen werden Oxidschichten in oxidierend eingestellten Plasmen als Haftvermittler eingesetzt, analog zu den üblichen Lackierverfahren, aber auch analog zur Oberflächenvorbereitung vor der Verklebung, die eine, meist mittels anodischer Oxidation erzeugte Oxidschicht benutzen. Die für eine gute Haftung wünschenswerte Aktivierung der Grenzfläche erfolgt, wenn überhaupt, durch Einlagerung artfremder Substanzen. In vielen Fällen wird die Anbindung ausschließlich über Adhäsionskräfte vorgenommen. Derartige Beschichtungs- oder Verklebungssysteme weisen erfahrungsgemäß nur mäßige Sicherheit gegen Unterwanderung auf, da durch Diffusion oder durch Permeationsvorgänge gebildeter Wasserdampf die Verbindung von Werkstoff und Beschichtung schwächt.In all experiments on aluminum materials that have become known so far become oxide layers in oxidizing plasmas as adhesion promoters used, analogous to the usual painting processes, but also analogous to Surface preparation before gluing, one, mostly by means of anodic Use oxidation-generated oxide layer. The one for good liability desirable activation of the interface occurs, if at all, by Storage of alien substances. In many cases the connection made exclusively via adhesive forces. Such coating experience has shown that there is only moderate security Infiltration due to diffusion or permeation processes formed water vapor the connection of material and coating weakens.

Andererseits ist die Plasmapolymerisation ein Verfahren, mit dem sich durch Einwirkung eines Plasmas auf organischem Molekül der Gasphase Festkörperbeschichtungen mit vorwiegend organischem Charakter und hervorragenden Eigenschaften erzeugen lassen. Die Plasmapolymerisation gehört zur Gruppe der Niederdruck-Plasmaprozesse und wird zunehmend industriell eingesetzt. Das großes Interesse an dieser Technologie ist auf die Vorteile eines schnellen, berührungslosen, trockenchemischen sowie das Werkstück wenig belastenden Beschichtungsverfahrens zurückzuführen.On the other hand, plasma polymerization is a process by which Exposure of a plasma to an organic molecule in the gas phase Solid coatings with predominantly organic character and excellent properties. Plasma polymerization belongs to the group of low pressure plasma processes and is growing used industrially. The great interest in this technology is due to the Advantages of a fast, contactless, dry chemical as well as that Part of the coating process that is not very stressful to the workpiece.

Mit Niedertemperaturplasmen abgeschiedene, plasmapolymere Schichten, im folgenden Plasmapolymere genannt, zeichnen sich wie folgt aus:

  • Plasmapolymere sind oft dreidimensional hoch vernetzt, unlöslich, kaum oder nicht quellend und potentielle gute Diffusionsbarrieren.
  • Sie sind verglichen mit konventionell hergestellten Polymeren aufgrund des hohen Vernetzungsgrades thermisch, mechanisch und chemisch ungewöhnlich stabil.
  • Die Schichten zeigen auf den meisten Substratmaterialien eine gute Haftung bei hoher Dichte und sind mikroporenfrei.
  • Die Schichten besitzen meistens eine amorphe Struktur und haben eine glatte, dem Substrat nachgebildete Oberfläche.
  • Die Schichten sind sehr dünn, die Schichtdicke beträgt nur bis zu einige 100 nm bis zu 10 nm.
  • Die Prozeßtemperaturen sind niedrig, Raumtemperatur bis ca. 100°C, insbesondere bis ca. 60°C.
Plasma polymer layers deposited with low temperature plasmas, hereinafter called plasma polymers, are characterized as follows:
  • Plasma polymers are often three-dimensionally highly cross-linked, insoluble, hardly or not swelling and potentially good diffusion barriers.
  • Due to the high degree of crosslinking, they are unusually thermally, mechanically and chemically stable compared to conventionally produced polymers.
  • The layers show good adhesion at high density on most substrate materials and are free of micropores.
  • The layers usually have an amorphous structure and have a smooth surface that mimics the substrate.
  • The layers are very thin, the layer thickness is only up to a few 100 nm up to 10 nm.
  • The process temperatures are low, room temperature up to approx. 100 ° C, especially up to approx. 60 ° C.

Andererseits sind bisher keine Verfahren bekannt geworden, mit denen Metallsubstrate, insbesondere Substrate aus Aluminiumwerkstoffen, korrosionsfest mit einem Plasmapolymeren beschichtet werden können.On the other hand, no methods have become known with which Metal substrates, in particular substrates made of aluminum materials, can be coated corrosion-resistant with a plasma polymer.

Rippenrohre aus dem Werkstoff AlMgSi0,5 werden vielfach in Brennwertkesseln verwandt. Solche Rippenrohre zeigen unter extremen Einsatzverhältnissen und in Grenzbereichen bezüglich der zugelassenen Gaszusammensetzung nicht immer eine ausreichende Korrosionsresistenz.Finned tubes made of AlMgSi0.5 are often used in condensing boilers related. Such finned tubes show under extreme conditions and not in limits with regard to the approved gas composition always sufficient corrosion resistance.

Die Bildung von Korrosionsprodukten führt auf der Gasseite im Bereich der Rippen zu Störungen, im fortgeschrittenen Stadium tritt zusätzlich zu einer Reduzierung der Wärmeaustauscherfläche auf der Brenngasseite auf.The formation of corrosion products leads on the gas side in the area of Ribs to disorders, in the advanced stage occurs in addition to one Reduction of the heat exchanger area on the fuel gas side.

Herkömmliche Korrosionsschutzmaßnahmen, die Stand der Technik sind, können aus mehreren Gründen nicht ergriffen werden. Verfahren wie Phosphatierung bzw. Chromatierung bedingen eine kontinuierlich Schwermetallionenemision an die Umgebung und scheiden aufgrund der zu erwartenden Verschärfung der Abwassergesetzgebung aus.Conventional corrosion protection measures that are state of the art, cannot be taken for several reasons. Procedures like Phosphating or chromating require a continuous Heavy metal ion emission to the environment and due to the expected tightening of wastewater legislation.

Lacksysteme kommen als Alternative ebenfalls nicht in Frage. Lacke als Oberflächenschutz führen zu einer Beeinträchtigung der Wärmeleitung, die im vorliegenden Fall nur in engen Grenze tolerierbar ist. Weiterhin führt bei herkömmlichen Lackbeschichtungen die Wasserdampfdiffusion zu Unterwanderung der Schutzschicht. Bei der anschließenden Kondensation auf der Metalloberfläche verursacht dies ein Abheben der Schicht und eine Beschleunigung des Korrosionsvorgangs, wie dies von lokalisierten Korrosionsarten bekannt ist.Paint systems are also not an alternative. Paints as Surface protection leads to an impairment of the heat conduction, which in the the present case can only be tolerated within a narrow limit. Furthermore, leads conventional lacquer coatings to water vapor diffusion Infiltration of the protective layer. During the subsequent condensation of the metal surface this causes the layer to lift off and one Accelerate the corrosion process, like this from localized Types of corrosion is known.

Eine Beschichtung solcher Rippenrohre für Wärmetauscher mit einem Plasmapolymeren wäre an und für sich wünschenswert. Diesbezügliche Versuche führten jedoch nicht zu korrosionsbeständigen Beschichtungen. In der Regel zeigte sich, daß die Plasmapolymere nicht fest genug an der Metalloberfläche hafteten und eine mehr oder weniger schnelle Unterwanderung der Beschichtung stattfand mit dem Ergebnis, daß es rasch zu Ablösungserscheinungen kommt.A coating of such finned tubes for heat exchangers with a Plasma polymers in and of themselves would be desirable. Attempts in this regard however did not lead to corrosion-resistant coatings. Usually showed that the plasma polymers were not strong enough on the metal surface stuck and a more or less rapid infiltration of the coating took place with the result that there are rapid signs of detachment.

Aus der DE-A-42 16 999 ist ein Verfahren zur Oberflächenbeschichtung von Silbergegenständen bekannt, bei dem die Oberfläche zunächst mit einem abtragenden Plasma behandelt und die Oberfläche anschließend mit einem Plasmapolymeren beschichtet wird, wobei zunächst eine Kopplungsschicht, darauf eine permeationsverhindernde Oberflächenschicht und schließlich eine Versiegelungsschicht erzeugt werden. Für die Kopplungsschicht kommen insbesondere Ethylen und Vinyltrimethylsilan zum Einsatz, für die permeationsverhindernde Schicht Ethylen und für die Versiegelung Hexamethyldisiloxan in Verbindung mit Sauerstoff als plasmabildende Monomere, wobei ein kontinuierlicher Übergang zwischen den plasmabildenden Monomeren stattfindet. Die Beschichtungen sind weitgehend kratzfest und bilden einen guten Anlaufschutz, können aber so eingestellt sein, daß sie mit einem Reinigungsmittel entfernt werden können. Eine Beschichtung von Aluminiumsubstraten führt nicht zu korrosionsbeständigen Beschichtungen.DE-A-42 16 999 describes a process for the surface coating of Silver objects known, in which the surface first with a removing plasma and then treating the surface with a Plasma polymer is coated, initially with a coupling layer, then a permeation-preventing surface layer and finally one Sealing layer are generated. Come for the coupling layer especially ethylene and vinyltrimethylsilane are used for which permeation-preventing layer of ethylene and for sealing Hexamethyldisiloxane in combination with oxygen as plasma-forming Monomers, with a continuous transition between the plasma-forming Monomers takes place. The coatings are largely scratch-resistant and form a good tarnish protection, but can be set so that with a cleaning agent can be removed. A coating of Aluminum substrates do not lead to corrosion-resistant coatings.

Insgesamt wäre es wünschenswert, über ein Verfahren zu verfügen, mit dem metallische Werkstoffe, insbesondere Aluminiumwerkstoffe dauerhaft und korrosionsfest mit einem Plasmapolymer beschichtet werden können. Overall, it would be desirable to have a process that metallic materials, especially aluminum materials durable and can be coated corrosion-resistant with a plasma polymer.

Diese Ziel wird mit einem Verfahren der eingangs genannten Art erreicht, bei dem das Substrat in einem Vorbehandlungsschritt einer mechanischen, chemischen und/oder elektrochemischen Glättung unterworfen wird und anschließend bei einer Temperatur von weniger als 200°C und einem Druck von 10-5 bis 100 mbar einem Plasma ausgesetzt wird, wobei in einem ersten Schritt in einem reduzierenden Plasma die Oberfläche aktiviert und in einem zweiten Schritt das Plasmapolymere aus einem Plasma, das wenigstens ggf. eine Sauerstoff, Stickstoff oder Schwefel enthaltende, unter den Bedingungen des Plasmas verdampfbare Kohlenwasserstoff- oder siliciumorganische Verbindung, die Fluoratome enthalten können, enthält, abgeschieden wird.This goal is achieved with a method of the type mentioned in the introduction, in which the substrate is subjected to mechanical, chemical and / or electrochemical smoothing in a pretreatment step and then at a temperature of less than 200 ° C. and a pressure of 10 -5 to 100 mbar is exposed to a plasma, in a first step activating the surface in a reducing plasma and in a second step the plasma polymer from a plasma which at least optionally contains an oxygen, nitrogen or sulfur which can be evaporated under the conditions of the plasma organosilicon compound, which may contain fluorine atoms, is deposited.

Es wurde überraschend gefunden, daß die Kombination einer glättenden Vorbehandlung des zu beschichtenden Metallsubstrats mit einer Plasmahandlung das Problem der mangelnden Haftung der Beschichtung auf der Metalloberfläche löst. Dabei besteht die Plasmabehandlung wiederum aus 2 Schritten, zum einen aus einer Behandlung der Oberfläche mit einem reduzierenden Plasma, das abtragend auf die Oberfläche einwirkt, und einem zweiten Schritt, in dem die eigentliche Beschichtung direkt auf die plasmavorbehandelte Metallschicht aufgebracht wird.It has surprisingly been found that the combination of a smoothing Pretreatment of the metal substrate to be coated with a Plasma handling the problem of lack of adhesion of the coating on the Metal surface detaches. The plasma treatment again consists of 2 Steps, firstly from a treatment of the surface with a reducing plasma, which removes the surface, and a second step in which the actual coating is applied directly to the plasma-pretreated metal layer is applied.

Die Vorbehandlung, insbesondere Glättung der Oberfläche des Metallsubstrat kann mit mechanischen, chemischen oder elektrochemischen Mitteln erfolgen. Besonders bevorzugt sind Kombinationen aus mechanischer und chemischer Glättung. Der mechanischen und/oder chemischen Glättung kann in jedem Fall eine elektrochemische Glättung nachgeschaltet werden, wenn das jeweilige Metallsubstrat dies zuläßt. Das Elektropolierverfahren ist beispielsweise bei Rippenrohren aus physikalisch/technischen Gründen nicht zur Oberflächenbehandlung geeignet. Hier ist man auf chemische Verfahren, wie saures oder alkalisches Beizen, angewiesen. Gemäß DE-C-40 39 479 kann auch ein Kombination aus Beizen in Verbindung mit einer mechanischen Störung der Oberfläche durch Wischen, Bürsten, Strahlen oder dergleichen zum Einsatz kommen, wobei insbesondere das Werkstück mit einem Flüssigkeitsstrahl, daß das Beizmittel sowie abbrasiv wirkende Partikel enthält, beaufschlagt wird.The pretreatment, especially smoothing the surface of the metal substrate can be done with mechanical, chemical or electrochemical means. Combinations of mechanical and chemical are particularly preferred Smoothing. The mechanical and / or chemical smoothing can in any case electrochemical smoothing can be added if the respective Metal substrate allows this. The electropolishing process is, for example, at Finned tubes not available for physical / technical reasons Suitable for surface treatment. Here you are on chemical processes like acidic or alkaline pickling. According to DE-C-40 39 479 can also a combination of pickling in connection with a mechanical malfunction of the Surface by wiping, brushing, blasting or the like come, in particular the workpiece with a liquid jet that contains the mordant and abrasive particles.

Bei dem zur Glättung der Oberfläche eingesetzten Beizverfahren handelt es sich um chemische Vorgänge, bei denen mit Hilfe aggressiver Chemikalien vornehmlich Oxid-, Rost- und Zunderschichten von der jeweiligen Metalloberfläche entfernt werden. Bei Beizflüssigkeiten handelt es sich meist um Säuren, die sowohl die Deckschichten als auch das Metall selbst angreifen. Das Beizen ist kein einheitlicher Vorgang. Vielmehr laufen verschieden chemische und physikalische Vorgänge nebeneinander und auch nacheinander ab. Die Vorgänge sind oft elektrochemischer Natur, wobei es zwischen den Metalloxiden und der Metalloberfläche zur Bildung von Lokalelementen kommt.The pickling process used to smooth the surface is to chemical processes involving aggressive chemicals mainly oxide, rust and scale layers of the respective Metal surface to be removed. Pickling liquids are mostly Acids that attack both the surface layers and the metal itself. The Pickling is not a uniform process. Rather, different chemical processes run and physical processes side by side and also one after the other. The Processes are often electrochemical in nature, being between the metal oxides and the metal surface to form local elements.

Das Elektropolieren ist ein Verfahren zum Glänzen von Metalloberflächen, bei dem Erhöhungen und Grate elektrolytisch abgetragen werden.Electropolishing is a process used to shine metal surfaces the ridges and ridges are removed electrolytically.

Insbesondere bei Aluminium ist das chemische Glanzbeizen als Verfahren zur Einebnung von Oberflächenrauhigkeiten weit entwickelt. Grundsätzlich hat es eine größere Bedeutung als das Elektropolieren. Es gibt eine Reihe chemischer Glanzbeizen für Aluminium.With aluminum in particular, chemical pickling is a process for Flattening of surface roughness well developed. Basically it has more important than electropolishing. There are a number of chemical ones Glossy stains for aluminum.

Die meisten chemischen Glanzlösungen sind auf Phosphorsäurebasis aufgebaut. Ein Zusatz von Salpetersäure bewirkt die Bildung spiegelnder Oberflächen und verbessert auch ihre Qualität. Die Zugabe von Schwefelsäure beschleunigt die Metallauflösung und verbessert die Einebnung. Weitere Zusätze können die Metallabtragsgeschwindigkeit weiter erhöhen und die Standzeiten des Bades verlängern.Most chemical gloss solutions are based on phosphoric acid. The addition of nitric acid causes the formation of reflective surfaces and also improves their quality. The addition of sulfuric acid accelerates the Metal dissolution and improves leveling. Other additives can Metal removal speed further increase and the service life of the bath extend.

Die Wirkung von Beizen, auch Glanzbeizen, läßt sich in Verbindung mit mechanischen Oberflächenbehandlungsverfahren weiter vergleichmäßigen und beschleunigen. Erfindungsgemäß kommt insbesondere eine solche Kombination von mechanischen und chemischen Oberflächenbehandlungsverfahren zur Glättung, wie sie in der DE-C-40 39 479 beschrieben sind, zum Einsatz.The effect of stains, including glossy stains, can be combined with mechanical surface treatment processes further uniform and accelerate. According to the invention, such a combination comes in particular of mechanical and chemical surface treatment processes for Smoothing, as described in DE-C-40 39 479, is used.

Aufgrund der amphoteren Eigenschaften von Aluminium und seiner Legierungen können dort auch alkalische Lösungen zum Reinigen und Beizen eingesetzt werden.Because of the amphoteric properties of aluminum and its Alloys can also use alkaline solutions for cleaning and pickling be used.

Im allgemeinen wird die Oberfläche durch die Glättungsbehandlung bis hin zu einem gemittelten Mittenrauhigkeit von weniger als 350 nm, vorzugsweise weniger als 250 nm geglättet. Durch Elektropolieren, insbesondere auch nachgeschaltetes Elektropolieren nach einer mechanisch/chemischen Glättung, können gemittelte Mittenrauhigkeit von weniger als 100 nm erreicht werden.In general, the surface is covered by the smoothing treatment an average roughness of less than 350 nm, preferably less than 250 nm smoothed. By electropolishing, especially downstream electropolishing after mechanical / chemical smoothing, average roughness of less than 100 nm can be achieved.

Die auf diese Art und Weise erzielten geglätteten Oberflächen sind allerdings immer noch nicht optimal für die Aufbringung eines Plasmapolymeren geeignet. Wird im Anschluß an die mechanische/chemische und/oder elektrochemische Glättung ein Plasmapolymeres aufgetragen, zeigt dies noch nicht die erwünschten Standzeiten unter korrosiven Bedingungen. Voraussetzung hierfür ist eine weitere Oberflächenbehandlung mittels eines reduktiv eingestellten Plasmas, insbesondere eines Wasserstoffplasmas. Diese Plasmabehandlung erfolgt bei Temperaturen von ≤ 200°C bei Drücken von ≤ 100 mbar, insbesondere bei ≤ 100°C und ≤ 10 mbar. Dem Wasserstoff als Träger des Plasmas können weitere Gase beigemischt werden, beispielsweise Kohlenwasserstoffe und insbesondere Olefine, wie nachstehend beschrieben, sowie Sauerstoff, Stickstoff oder auch Argon, wobei darauf zu achten ist, daß der reduzierende Charakter beibehalten wird.However, the smoothed surfaces achieved in this way are still not optimally suited for the application of a plasma polymer. Will follow the mechanical / chemical and / or electrochemical Smoothing a plasma polymer applied, this does not show the desired service life under corrosive conditions. Prerequisite for this is a further surface treatment using a reductively set Plasma, especially a hydrogen plasma. This plasma treatment takes place at temperatures of ≤ 200 ° C at pressures of ≤ 100 mbar, in particular at ≤ 100 ° C and ≤ 10 mbar. The hydrogen as a carrier of the plasma can other gases are added, for example hydrocarbons and in particular olefins, as described below, and oxygen, nitrogen or also argon, taking care that the reducing character is maintained.

Das Ergebnis dieser Plasmabehandlung ist die Erzielung einer aktivierten Oberfläche. Unter den reduzierenden Bedingungen wird vermutlich eine Verringerung der Aluminiumoxidschicht und/oder oberflächennaher Aluminiumhydroxide auf der Metalloberfläche herbeigeführt, so daß sich Ansatzpunkte für eine reaktive Anbindung eines später aufgebrachten Plasmapolymeren direkt an das Metall ergeben. Weiterer Nebeneffekt ist, daß die Oberfläche durch die Plasmabehandlung weiter geglättet wird.The result of this plasma treatment is the achievement of an activated one Surface. Under the reducing conditions, presumably one Reduction of the aluminum oxide layer and / or near the surface Aluminum hydroxides brought about on the metal surface, so that Starting points for a reactive connection of a later one Plasma polymers directly to the metal. Another side effect is that the Surface is further smoothed by the plasma treatment.

Auf die plasmabehandelte Oberfläche wird, vorzugsweise zunächst unter weiter reduzierenden Bedingungen, ein Plasmapolymeres niedergeschlagen. Als Hauptbestandteil dieses Plasmapolymers dient Kohlenwasserstoff- und/oder eine siliciumorganische Verbindung, die Sauerstoff-, Stickstoff- oder Schwefelatome enthalten kann, wobei diese Kohlenwasserstoff- oder siliciumorganische Verbindung einen Siedepunkt aufweist, das sie unter den in der Plasmabeschichtungskammer herrschenden Temperatur- und Druckbedingungen verdampfbar ist. In erster Linie kommen hierfür Alkane, Alkene, aromatische Kohelwasserstoffe, Silane, Siloxane, Silazane und Silathiane in Frage, vorzugsweise Siloxane. Besonders bevorzugt ist der Einsatz von Hexamethyldisiloxan und Hexamethylcyclotrisiloxan. Andere Verbindungen sind Hexamethyldisilazan und Hexamethylcyclotrisilazan, wie auch Hexamethyldisilathian. Einsetzbar sind auch höhere Homologe dieser Verbindungen und Mischungen solcher Verbindungen, ebenso wie die teilweise oder vollständig fluorierten Derivate.On the plasma-treated surface is, preferably first under further reducing conditions, a plasma polymer put down. As The main component of this plasma polymer is hydrocarbon and / or organosilicon compound, the oxygen, nitrogen or sulfur atoms May contain, these hydrocarbon or organosilicon Compound has a boiling point, which it under the in the Plasma coating chamber prevailing temperature and Pressure conditions is evaporable. Primarily alkanes come for this, Alkenes, aromatic hydrocarbons, silanes, siloxanes, silazanes and silathiane in question, preferably siloxanes. The use of is particularly preferred Hexamethyldisiloxane and hexamethylcyclotrisiloxane. Other connections are Hexamethyldisilazane and hexamethylcyclotrisilazane as well Hexamethyldisilathiane. Higher homologues of these can also be used Compounds and mixtures of such compounds, as well as those in part or fully fluorinated derivatives.

Als Co-Monomer für die Bildung des Plasmapolymeren aus siliciumorganischen Monomeren kommen Kohlenwasserstoffe, insbesondere Olefine in Frage, beispielsweise Ethylen, Propen und Cyclohexen. Silane, insbesondere vinylhaltige siliciumorganische Verbindungen können ebenfalls als Co-Monomere eingesetzt werden, beispielsweise Vinyltrimethylsilazan. Diese ungesättigten Monomeren können der O-, N- oder S-Atom-haltigen siliciumorganischen Verbindung in festen oder sich ändernden Anteilen zugemischt werden, wobei eine abgestufte Zumischung in Frage kommt. Beispielsweise kann bei stufenweisem Aufbau des Plasmapolymeren zunächst eine Übergangsschicht auf der Metalloberfläche aufgebaut werden, die ausschließlich oder überwiegend aus der siliciumorganischen Verbindung besteht, und anschließend der Kohlenwasserstoff zugemischt werden. Die umgekehrte Verfahrensweise ist ebenfalls möglich. Auf diese Art und Weise lassen sich die Eigenschaften der Plasmapolymerbeschichtung dahingehend verändern, daß eine optimale Anheftung an das Metallsubstrat und/oder eine optimale Beständigkeit gegen korrodierende Substanzen gegeben ist. Ein solch gradierter Aufbau ist beispielsweise aus der DE-A-42 16 999 bekannt.As a co-monomer for the formation of the plasma polymer from organosilicon Monomers are hydrocarbons, especially olefins, for example ethylene, propene and cyclohexene. Silanes, in particular Vinyl-containing organosilicon compounds can also be used as co-monomers are used, for example vinyltrimethylsilazane. This unsaturated monomers can contain O, N or S atoms Organosilicon compound in fixed or changing proportions be admixed, a graded admixture being considered. For example, with a step-by-step build-up of the plasma polymer a transition layer can be built up on the metal surface exclusively or predominantly from the organosilicon compound exists, and then the hydrocarbon is added. The reverse procedure is also possible. That way The properties of the plasma polymer coating can be change that optimal attachment to the metal substrate and / or optimal resistance to corrosive substances is given. Such Graded structure is known for example from DE-A-42 16 999.

Bei der Plasmapolymerisation können zusätzlich zu diesen Monomeren weitere Gase eingespeist werden, beispielsweise Sauerstoff, Stickstoff oder Argon, um die Eigenschaften des Plasmas und des Plasmapolymeren zu beeinflussen.In addition to these monomers, plasma polymerization can include other Gases are fed, for example oxygen, nitrogen or argon, around the To influence properties of the plasma and the plasma polymer.

Die Plasmapolymerisation findet im allgemeinen bei einer Temperatur von ≤ 200°C, vorzugsweise ≤ 100°C und insbesondere etwa 60°C statt. Der Druck in der Plasmabeschichtungskammer liegt im allgemeinen bei ≤ 10 mbar.Plasma polymerization generally takes place at a temperature of ≤ 200 ° C, preferably ≤ 100 ° C and in particular about 60 ° C instead. The pressure in the Plasma coating chamber is generally ≤ 10 mbar.

Die durch die Plasmapolymerbildung gebildete Schicht auf dem Metallsubstrat hat zweckmäßigerweise eine Dicke von 100 nm bis 10 µm. Es ist aber ohne weiteres möglich, für besondere Zwecke Schichtdicken von weniger als 100 nm zu erzeugen.The layer formed by the plasma polymer formation on the metal substrate suitably has a thickness of 100 nm to 10 microns. But it is without further possible to use layer thicknesses of less than 100 nm for special purposes produce.

Im Gegensatz zu anderen Beschichtungen, auch anders aufgebrachten Plasmapolymerbeschichtungen, wird erfindungsgemäß eine Glättung der Oberfläche durch eine einebnende Beizung erzielt, deren Wirkung durch einen überlagerte leichte mechnische Komponente gesteigert und vergleichmäßigt wird. Es kommt daher weniger zu einer mechanischen Verklammerung der Polymerbeschichtung auf dem Metallsubstrat aufgrund einer relativ hohen Rauhigkeit des Substrats, sondern vielmehr zu einer eher chemischen Anbindung an freie Valenzen der freigelegten und freigeätzten Metalloberfläche. Es wird im allgemeinen eine nahezu spiegelblanke, optisch ansprechende Oberfläche auf nicht strukturierten Metalloberflächen erreicht. Insbesondere wird erreicht, daß die Beschichtung von ihrer Dicke her nicht mehr in den Oberflächenstrukturen einer rauhen Metalloberfläche "untergeht", sondern eine gleichmäßige, ebene Schicht entsteht.In contrast to other coatings, also applied differently Plasma polymer coatings, according to the invention, is a smoothing of the Surface achieved by a leveling dressing, the effect of which by a superimposed light mechanical component is increased and evened out. There is therefore less mechanical clamping of the Polymer coating on the metal substrate due to a relatively high Roughness of the substrate, but rather a more chemical one Connection to free valences of the exposed and etched metal surface. It is generally an almost mirror-bright, visually appealing Surface reached on unstructured metal surfaces. In particular is achieved that the thickness of the coating no longer in the Surface structures of a rough metal surface "go down", but one uniform, even layer is created.

Eine im Vergleich zur technischen Oberfläche um ein Mehrfaches gesteigerte Korrosionsschutzwirkung wurde erfindungsgemäß erzielt.One that is several times higher than the technical surface Corrosion protection effect was achieved according to the invention.

Eine weitere Steigerung der Langzeitkorrosionsbeständigkeit wird durch den Einbau eines im Vakuum verdampfbaren Korrosionsinhibitors in vorzugsweise die unterste Lage der plasmapolymeren Beschichtung erzielt. Im Gegensatz zu bisher vorliegenden Ergebnissen ist es nicht wesentlich, daß ein solcher Korrosionsinhibitor direkt auf die Substratoberfläche aufgebracht wird, also nicht direkt in der Haftungsebene liegt und diese dadurch schwächt. Vielmehr wird eine Fernwirkung erzielt, die insbesondere mit der Verwendung leitfähiger Polymere verbunden ist. Geeignete solche Polymere sind beispielsweise Polyaniline, die im Vakuum einen geringen Dampfdruck haben oder in feinstverteilter Form in das Plasmapolymer eingebracht werden können, in einer Menge von 0,1 bis 1 Gew.-%.A further increase in long-term corrosion resistance is achieved by the Installation of a corrosion inhibitor which can be evaporated in vacuo, preferably achieved the lowest layer of the plasma polymer coating. In contrast to so far it is not essential that such Corrosion inhibitor is applied directly to the substrate surface, ie is not directly in the liability level and weakens it. Much more a long-distance effect is achieved, especially with the use of conductive Polymers is connected. Suitable such polymers are, for example Polyanilines that have a low vapor pressure in vacuum or in finely divided form can be introduced into the plasma polymer, in one Amount from 0.1 to 1% by weight.

Über den Einsatz auf Aluminiumwerkstoffe hinaus ist die beschriebene Technologie auf weitere metallische Werkstoffe, insbesondere solche, die zur Ausbildung einer Oberflächenoxidschicht neigen, anwendbar.In addition to the use on aluminum materials, the described is Technology on other metallic materials, especially those that are used for Formation of a surface oxide layer tend to be applicable.

Das erfindungsgemäße Verfahren kann weiterhin dazu eingesetzt werden, eine plasmapolymere Grundierung auf ein Metallsubstrat aufzubringen, die dann anschließend durch weitere Beschichtungen ergänzt wird. Hierdurch können korrosionsfeste Beschichtungen für verschiedenste Zwecke mit hoher Beschichtungsdicke erzielt werden, die genügend Schichtdicke für eine abrasive Beanspruchung haben. Besonders gut hierfür geeignet sind Ormocere. Beschichtungen von Ormoceren haben von ihrem strukturellen Aufbau her Ähnlichkeit mit hochvernetzten plasmapolymeren Beschichtungen, können jedoch ohne den relativ langsamen Beschichtungsprozess im Vakuum aufgebaut werden. Die typischen Schichtdicken liegen hierbei in der Größenordnung von 1 bis 100 nm. Mit der Kombination sind ähnlich gute Korrosionseigenschaften zu erzeilen wie mit plasmapolymeren Beschichtungen allein.The method according to the invention can also be used to: applying plasma polymeric primer to a metal substrate, which then is then supplemented by further coatings. This can corrosion-resistant coatings for various purposes with high Coating thickness can be achieved, the enough layer thickness for an abrasive Have stress. Ormocere are particularly well suited for this. Ormoceren coatings have a structural structure Similarity to highly cross-linked plasma polymer coatings, can but built up in vacuum without the relatively slow coating process become. The typical layer thicknesses are of the order of 1 up to 100 nm. The combination offers similarly good corrosion properties as with plasma polymer coatings alone.

Insbesondere ist das erfindungsgemäße Verfahren zur Beschichtung von Aluminiumwerkstoffen geeignet, wobei die erzielte Korrosionsbeständigkeit den Aluminiumwerkstoff besonders für den Einsatz als Wärmetauscher und zur Herstellung von Rippenrohren für Wärmetauscher in Brennwertkesseln geeignet macht.In particular, the inventive method for coating Suitable aluminum materials, the corrosion resistance achieved Aluminum material especially for use as a heat exchanger and for Production of finned tubes suitable for heat exchangers in condensing boilers makes.

Beispielexample

Als Testmaterial wurden Rechteckproben aus dem Werkstoff AlMgSi0,5 verwandt. Die Proben wurden zunächst einem mehrstufigen Reinigungsverfahren unterworfen, um Fremstoffe, wie Öle und Fette zu entfernen. Anschließend wurde die Oberfläche der Bleche mit einem kombinierten Beiz- und Elektropolierverfahren behandelt.Rectangular samples made of AlMgSi0.5 were used as test material related. The samples were initially a multi-stage Subject to cleaning procedures to remove foreign matter such as oils and fats remove. Then the surface of the sheets was cleaned with a combined pickling and electropolishing processes.

Die Proben wurden zunächst mittels Bürste in einer pH-neutralen Seifenlaugelösung mechanisch gereinigt, danach abgespült, und erneut in der Seifenlaugenlösung 30 min. bei t = 70°C im Ultraschallbad behandelt. Nach weiterem Abspülen mit fließendem Wasser und Trocknen mit Heißluft wird im Ultraschallbad mit Aceton reinst entfettet und mit Heißluft getrocknet.The samples were first brushed in a pH neutral Soapy water solution mechanically cleaned, then rinsed off, and again in the Soapy water solution 30 min. treated at t = 70 ° C in an ultrasonic bath. To further rinsing with running water and drying with hot air is carried out in the Ultra-degreased ultrasonic bath with acetone and dried with hot air.

Anschließend werden die Metallproben in einer Beize aus 46,0 Teilen Wasser, 50,0 Teilen konzentrierte Salpetersäure und 4,0 Teilen Flußsäure bei Raumtemperatur 120 s gebeizt. Nach Abspülen mit Wasser und Ethanol wurde das Werkstück dann elektrochemisch poliert. Als Elektrolyt diente eine Mischung aus 78 ml 70 bis 72 %-ige Chlorsäure, 120 ml aqua dest, 700 ml Ethanol und 100 ml Butylglykol. Das Eletropolieren wurde über einen Zeitraum von 180 s bei einer Elektrolyttemperatur von -15 bis + 8°C, einem Polierstrom von 5 bis 18 A/dm2 und einer Polierspannung von 19 bis 11 V durchgeführt.The metal samples are then pickled in a pickle consisting of 46.0 parts of water, 50.0 parts of concentrated nitric acid and 4.0 parts of hydrofluoric acid at room temperature for 120 s. After rinsing with water and ethanol, the workpiece was then polished electrochemically. A mixture of 78 ml of 70 to 72% chloric acid, 120 ml of distilled water, 700 ml of ethanol and 100 ml of butyl glycol was used as the electrolyte. The electropolishing was carried out over a period of 180 s at an electrolyte temperature of -15 to + 8 ° C, a polishing current of 5 to 18 A / dm 2 and a polishing voltage of 19 to 11 V.

Unmittelbar nach dem Elektropolieren wurde die Probe mit Wasser abgespült und im Ultraschallbad 10 min. in kaltem Wasser behandelt. Zum Schluß wurde mit Heißluft getrocknet.Immediately after electropolishing, the sample was rinsed off with water and in the ultrasonic bath 10 min. treated in cold water. In the end dried with hot air.

Vor der Oberflächenglättung hatte das Werkstück eine matte Oberfläche mit einer Mittenrauhigkeit von 0,570 µm (gemittelt aus 5 Messungen). Nach der Elektropolitur betrug die Mittenrauhigkeit weniger als 100 nm. Die Oberfläche war hochglänzend.Before the surface was smoothed, the workpiece had a matt surface an average roughness of 0.570 µm (averaged over 5 measurements). After The electropolishing roughness was less than 100 nm. The surface was shiny.

Die Plasmabehandlung wurde in einer üblichen Plasmapolymerisationsanlage durchgeführt, bei der in den Unterdruckbehälter das monomere Gas eingeführt und durch hoch frequenten Wechselstrom und/oder Mikrowellenenergie zur Plasmabildung angeregt wurde.The plasma treatment was carried out in a conventional plasma polymerization plant performed, in which the monomer gas is introduced into the vacuum tank and by high frequency alternating current and / or microwave energy for Plasma formation was stimulated.

In dem ersten Schritt der Plasmabehandlung wurde das Aluminiumwerkstück bei 60°C und 50 mbar 120 s mit einem Wasserstoffplasma beaufschlagt. Der Wasserstoff wurde sukzessive durch Einspeisung von Hexamethyldisiloxan bei einem Druck von 10 mbar ersetzt. Der Volumenstrom betrug zu 500 ml/min., die Leistung lag bei max. 5 KW. Die Auftragung erfolgte in einer Schichtdicke von 500 nm.In the first step of the plasma treatment, the aluminum workpiece at 60 ° C and 50 mbar for 120 s with a hydrogen plasma. The Hydrogen was gradually added by feeding in hexamethyldisiloxane a pressure of 10 mbar. The volume flow was 500 ml / min Output was max. 5 KW. The application took place in a layer thickness of 500 nm.

Das Beispiel wurde dahingehend variiert, daß bei der Plasmapolymerisation zunächst auf die Metalloberfläche ein Plasmapolymeres aus Ethylen als Monomer aufgebracht wurde, dem in zunehmenden Mengen Hexamethyldisiloxan zugemischt wurde, bis das Ethylen vollständig verdrängt war. The example was varied in that the plasma polymerization first on the metal surface as a plasma polymer made of ethylene Monomer was applied in increasing amounts Hexamethyldisiloxane was added until the ethylene was completely displaced was.

In weiteren Versuchen wurden den Monomeren als Zusatzgase Sauerstoff und Stickstoff beigemischt.In further experiments, the monomers were oxygen and Nitrogen added.

In allen diesen Verfahren wurden hoch korrosionsfeste, dünne, transparente Schichten auf der Oberfläche des Aluminiumbleches abgeschieden, das seinen hochglänzenden Charakter behielt.In all of these processes, highly corrosion-resistant, thin, transparent Layers deposited on the surface of the aluminum sheet, its retained its high-gloss character.

Durch Elektronenmikroskopie wurde festgestellt, daß die plasmapolymere Schicht eine gute Anbindung an die Metalloberfläche besitzt. Die plasmapolymere Schicht ist amorph und praktisch fehlerfrei, d. h. sie weist keine Poren oder Einschlüsse auf.It was found by electron microscopy that the plasma polymers Layer has a good connection to the metal surface. The Plasma polymer layer is amorphous and practically free of defects, i. H. she has none Pores or inclusions.

Das Korrosionsverhalten der so beschichteten Aluminiumbleche wurde in 25 %-iger Schwefelsäure bei Raumtemperatur und 60 bis 70°C sowie in 20 %-iger Salpetersäure bei Raumtemperatur geprüft. Alle Proben erwiesen sich in den über mehrere Stunden durchgeführten Tests als beständig. Es trat keine Einwanderung der Testflüssigkeit in die Beschichtung oder gar Unterwanderung der Beschichtung durch die Flüssigkeit auf. Ablösungserscheinungen wurden nicht beobachtet.The corrosion behavior of the aluminum sheets coated in this way became 25% Sulfuric acid at room temperature and 60 to 70 ° C and in 20% Nitric acid tested at room temperature. All samples were found in the tests carried out over several hours as stable. There was none Immigration of the test liquid into the coating or even infiltration the coating through the liquid. Signs of detachment were not observed.

Die erfindungsgemäß beschichteten Aluminiumbleche erwiesen sich bei 350°C unter Bedingungen, wie sie in einem Wärmetauscher für Brennwertkessel herrschen, absolut beständig. Sie weisen zudem eine herabgesetzte Oberflächenspannung auf, weshalb eine geringere Tendenz zu mineralischen Anlagerungen, beispielsweise in Form von Kesselstein, besteht. Die herabgesetzte Oberflächenspannung schützt auch vor biologischem Bewuchs, beispielsweise bei Werkstücken, die Seewasser ausgesetzt sind,The aluminum sheets coated according to the invention proved to be at 350 ° C under conditions such as those in a heat exchanger for condensing boilers rule, absolutely constant. They also show a degraded Surface tension, which is why there is a lower tendency to mineral Deposits, for example in the form of scale, exist. The reduced surface tension also protects against biological growth, for example, for workpieces that are exposed to sea water,

Claims (19)

  1. A method for corrosion-resistant coating of metal substrates by means of plasma polymerisation, characterized in that the substrate is subjected in a preliminary treatment step to mechanical, chemical and/or electrochemical smoothing and is then exposed to a plasma at a temperature of less than 200 °C and a pressure from 10-5 to 100 mbar, wherein the surface is activated in a first step in a reducing plasma and a plasma polymer is deposited in a second step from a plasma which contains at least one hydrocarbon or organo-silicon compound, which can contain fluorine atoms, which can be vaporised under the conditions of the plasma and which optionally contains oxygen, nitrogen or sulphur.
  2. A method according to claim 1, characterized in that the metal substrate is aluminium or an aluminium alloy.
  3. A method according to claim 1 or 2, characterized in that the metal substrate is subjected to a combination of mechanical surface treatment and etching.
  4. A method according to any of the preceding claims, characterized in that the metal substrate is electrochemically polished.
  5. A method according to any of the preceding claims, characterized by an average mean roughness of the metal substrate after the smoothing treatment of less than 350 nm.
  6. A method according to any of the preceding claims, characterized in that the plasma treatment is effected at a temperature of ≤ 100 °C.
  7. A method according to any of the preceding claims, characterized in that in that the surface is activated with a hydrogen plasma at a pressure ≤ 100 mbar in the first step of the plasma treatment.
  8. A method according to any of the preceding claims, characterized in that the organo-silicon compound in the second step of the plasma treatment contains a siloxane, silazane or silathiane.
  9. A method according to claim 8, characterized in that a siloxane, especially hexamethyldisiloxane or hexamethylcyclotrisiloxane is used.
  10. A method according to any of the preceding claims, characterized in that the plasma contains a hydrocarbon, especially an olefin.
  11. A method according to claim 10, characterized in that the hydrocarbon is ethylene, propylene or cyclohexene.
  12. A method according to any of the preceding claims, characterized in that the separating out in the second plasma treatment step takes place at a pressure of ≤ 10 mbar under initially reducing conditions.
  13. A method according to any of the preceding claims, characterized in that oxygen, nitrogen and/or a noble gas is fed into the plasma.
  14. A method according to any of the preceding claims, characterized in that the plasma polymer coating is applied to a thickness of 100 nm to 1 µm.
  15. A method according to any of the preceding claims, characterized in that a corrosion inhibitor is introduced to the plasma polymer.
  16. A method according to claim 15, characterized in that the corrosion inhibitor is a polyaniline in an amount from 0.1 to 1% by weight.
  17. A method according to any of the preceding claims, characterized in that the plasma coated metal substrate is provided with a further coating.
  18. Use of the method according to any of the preceding claims on an aluminium heat exchanger, especially in the form of finned tubes.
  19. A metal substrate with a corrosion-resistant coating, characterized in that it is obtainable according to a method according to any of claims 1 to 17.
EP19980961076 1997-10-31 1998-10-29 Method for corrosion-resistant coating of metal substrates by means of plasma polymerisation Expired - Lifetime EP1027169B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19748240A DE19748240C2 (en) 1997-10-31 1997-10-31 Process for the corrosion-resistant coating of metal substrates by means of plasma polymerization and its application
DE19748240 1997-10-31
PCT/DE1998/003266 WO1999022878A2 (en) 1997-10-31 1998-10-29 Method for corrosion-resistant coating of metal substrates by means of plasma polymerisation

Publications (2)

Publication Number Publication Date
EP1027169A2 EP1027169A2 (en) 2000-08-16
EP1027169B1 true EP1027169B1 (en) 2002-01-09

Family

ID=7847280

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19980961076 Expired - Lifetime EP1027169B1 (en) 1997-10-31 1998-10-29 Method for corrosion-resistant coating of metal substrates by means of plasma polymerisation

Country Status (13)

Country Link
US (2) US6242054B1 (en)
EP (1) EP1027169B1 (en)
JP (1) JP4263353B2 (en)
KR (1) KR100377025B1 (en)
AT (1) ATE211660T1 (en)
AU (1) AU1662699A (en)
CZ (1) CZ297047B6 (en)
DE (2) DE19748240C2 (en)
DK (1) DK1027169T3 (en)
ES (1) ES2172252T3 (en)
HU (1) HUP0401917A3 (en)
NO (1) NO326804B1 (en)
WO (1) WO1999022878A2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010039939A1 (en) 2010-08-30 2012-03-01 Aktiebolaget Skf Method of adhesive coating a metallic substrate
DE102018212540A1 (en) * 2018-07-27 2020-01-30 Bayerische Motoren Werke Aktiengesellschaft Method for coating a motor vehicle raw component and motor vehicle raw component

Families Citing this family (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020189931A1 (en) * 1997-12-04 2002-12-19 Korea Institute Of Science And Technology Plasma polymerization enhancement of surface of metal for use in refrigerating and air conditioning
KR19990047370A (en) * 1997-12-04 1999-07-05 구자홍 Refrigeration and air conditioning metal materials with improved hydrophilicity or hydrophobicity of the surface and methods for improving the same
US6105588A (en) * 1998-05-27 2000-08-22 Micron Technology, Inc. Method of resist stripping during semiconductor device fabrication
DE19835883A1 (en) * 1998-08-07 2000-02-17 Siemens Ag Manufacturing process for an electrical insulator
DE19924108B4 (en) * 1999-05-26 2007-05-03 Robert Bosch Gmbh Plasma polymer coating and process for its preparation
US6523615B2 (en) * 2000-03-31 2003-02-25 John Gandy Corporation Electropolishing method for oil field tubular goods and drill pipe
US20030042129A1 (en) * 2000-04-06 2003-03-06 Korea Institute Of Science And Technology Plasma polymerization enhancement of surface of metal for use in refrigerating and air conditioning
DE10131156A1 (en) 2001-06-29 2003-01-16 Fraunhofer Ges Forschung Articles with a plasma polymer coating and process for its production
JP2003088748A (en) * 2001-09-18 2003-03-25 Denso Corp Production method for polyaniline film and heat exchanger having polyaniline film
KR100438940B1 (en) * 2001-10-12 2004-07-03 주식회사 엘지이아이 Anti-corrosion treatment method of metal using plasma
US6875480B2 (en) * 2002-02-27 2005-04-05 Industrial Technology Research Institute Method of enhancement of electrical conductivity for conductive polymer by use of field effect control
US6869818B2 (en) * 2002-11-18 2005-03-22 Redwood Microsystems, Inc. Method for producing and testing a corrosion-resistant channel in a silicon device
JP3946130B2 (en) * 2002-11-20 2007-07-18 東京エレクトロン株式会社 Plasma processing apparatus and plasma processing method
US7482249B2 (en) * 2002-11-29 2009-01-27 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Method and device for machining a wafer, in addition to a wafer comprising a separation layer and a support layer
DE10342448A1 (en) * 2003-09-13 2005-04-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Anticorrosion coating
WO2005033663A2 (en) * 2003-09-30 2005-04-14 Sequenom, Inc. Methods of making substrates for mass spectrometry analysis and related devices
DE102004013306A1 (en) * 2004-03-17 2005-10-06 Behr Gmbh & Co. Kg coating process
US7673970B2 (en) * 2004-06-30 2010-03-09 Lexmark International, Inc. Flexible circuit corrosion protection
US7561717B2 (en) * 2004-07-09 2009-07-14 United Parcel Service Of America, Inc. System and method for displaying item information
US8134292B2 (en) * 2004-10-29 2012-03-13 Ledengin, Inc. Light emitting device with a thermal insulating and refractive index matching material
KR100698462B1 (en) * 2005-01-06 2007-03-23 (주)셀시아테크놀러지스한국 Flat panel type heat transfer device using hydrophilic wick, manufacturing method thereof and chip set comprising the same
WO2007051803A1 (en) * 2005-10-31 2007-05-10 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Mould-release coating and method for producing said coating
DE102005052409B3 (en) * 2005-10-31 2007-07-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Coating method for coating of surface, involves application of low-energy undercoating on surface which is to be coated and subsequently applying of layer containing or consisting of cross-linkable substance
US8201619B2 (en) 2005-12-21 2012-06-19 Exxonmobil Research & Engineering Company Corrosion resistant material for reduced fouling, a heat transfer component having reduced fouling and a method for reducing fouling in a refinery
EP1979700A2 (en) 2005-12-21 2008-10-15 ExxonMobil Research and Engineering Company Corrosion resistant material for reduced fouling, heat transfer component with improved corrosion and fouling resistance, and method for reducing fouling
DE102006018491A1 (en) * 2006-04-19 2007-10-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Flexible plasma polymer products, corresponding articles, manufacturing methods and use
DE102006028809B4 (en) * 2006-06-21 2015-10-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. A wafer carrier assembly, laminate for use in making such a wafer carrier assembly, and related methods and uses
US9365931B2 (en) * 2006-12-01 2016-06-14 Kobe Steel, Ltd. Aluminum alloy with high seawater corrosion resistance and plate-fin heat exchanger
DE102007010071A1 (en) 2007-02-28 2008-09-04 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Layer composite for transmission of lacquer on substrate, producing fiber-reinforced plastics, has lacquer coating and interlayer, where lacquer coating has soft or partly hardened or hardened lacquer
DE102007020655A1 (en) 2007-04-30 2008-11-06 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for producing thin layers and corresponding layer
DE102007040655B4 (en) 2007-08-27 2011-07-14 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 80686 Function layer transfer arrangement, method for its production, transfer method for a functional layer and use of a plasma polymer layer or a functional layer transfer arrangement for transferring a functional layer to a substrate
US7732068B2 (en) * 2007-08-28 2010-06-08 Alcoa Inc. Corrosion resistant aluminum alloy substrates and methods of producing the same
US8309237B2 (en) * 2007-08-28 2012-11-13 Alcoa Inc. Corrosion resistant aluminum alloy substrates and methods of producing the same
EP2047981B1 (en) * 2007-09-20 2010-11-03 Kabushiki Kaisha Kobe Seiko Sho Aluminum alloy material having an excellent sea water corrosion resistance and plate heat exchanger
DE102007000611A1 (en) 2007-10-31 2009-05-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Scratch-resistant and stretchable corrosion protection layer for light metal substrates
US20090162544A1 (en) * 2007-12-20 2009-06-25 Garesche Carl E Method of surface coating to enhance durability of aesthetics and substrate component fatigue
ITMI20080773A1 (en) * 2008-04-24 2009-10-25 Moma S R L DEVICE FOR THERMO-HYDRAULIC APPLICATIONS WITH IMPROVED ANTI-SCALE PROPERTIES AND RELATED METHOD OF ACHIEVEMENT
JP5160981B2 (en) * 2008-07-10 2013-03-13 株式会社神戸製鋼所 Aluminum alloy material with excellent corrosion resistance and plate heat exchanger
DE102009000821B4 (en) * 2009-02-12 2013-05-02 Surcoatec Ag A method for applying a coating to workpieces and / or materials comprising at least one easily oxidizable non-ferrous metal and workpiece and / or material produced by the method
DE102009002780A1 (en) 2009-04-30 2010-11-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Metal substrates with a scratch-resistant and elastic corrosion protection layer and process for their production
DE102010044114A1 (en) 2010-11-18 2012-05-24 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for joining substrates and composite structure obtainable therewith
US8840970B2 (en) 2011-01-16 2014-09-23 Sigma Laboratories Of Arizona, Llc Self-assembled functional layers in multilayer structures
JP5678823B2 (en) * 2011-07-06 2015-03-04 豊田合成株式会社 Composite of metal and resin and method for producing the same
US20140113146A1 (en) * 2012-10-24 2014-04-24 Ford Global Technologies, Llc Coated Metallic Parts and Method of Making The Same
DE102013215919B3 (en) * 2013-08-12 2015-02-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Color-neutral coated metal-containing article with metal-containing or metal surface, process for its preparation and use of a corresponding color-neutral coating
DE112014003722A5 (en) * 2013-08-12 2016-04-28 Wieland-Werke Ag Coating for antimicrobial surfaces
DE102013215912B3 (en) * 2013-08-12 2015-02-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Color-neutral coated copper-containing article, process for its preparation and use of a corresponding color-neutral coating
DE102013014040B4 (en) 2013-08-22 2018-10-11 Audi Ag Foil laminate for application to a disc or visor
DE102013219337B3 (en) * 2013-09-25 2015-04-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Plasma polymer solid, in particular plasma polymer layer, their preparation and their use as corrosion protection
DE102014219979A1 (en) 2014-10-01 2016-04-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Composite of substrate, plasma polymer layer, mixed layer and cover layer
US9968963B2 (en) 2015-08-31 2018-05-15 Sigma Laboratories Of Arizona, Llc Functional coating
DE102015115167B4 (en) 2015-09-09 2017-03-30 Lisa Dräxlmaier GmbH Shaped body comprising a functional layer, process for its preparation and its use
DE102017201559A1 (en) 2017-01-31 2018-08-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Atmospheric pressure plasma process for the production of plasma polymer coatings
DE102017130353A1 (en) 2017-12-18 2019-06-19 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Sol-gel based primer layer for PTFE-based coatings and methods of making same
DE102018131228A1 (en) 2018-12-06 2020-06-10 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Contact point for an electrical contact
DE102019101061B4 (en) * 2019-01-16 2022-02-17 Infineon Technologies Ag METHOD OF FORMING CONTACT STRUCTURE, METHOD OF FORMING CHIP PACKAGE AND CHIP PACKAGE
JP7310685B2 (en) * 2020-04-02 2023-07-19 トヨタ自動車株式会社 Corrosion-resistant film forming method, corrosion-resistant member having corrosion-resistant film formed thereon, heat exchanger, and fuel cell system

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4125152A (en) * 1977-09-19 1978-11-14 Borg-Warner Corporation Scale resistant heat transfer surfaces and a method for their preparation
US4391843A (en) * 1981-08-14 1983-07-05 Rca Corporation Adherent perfluorinated layers
US4503099A (en) * 1983-06-15 1985-03-05 Borg-Warner Corporation Heat transfer surfaces having scale resistant polymer coatings thereon
US4524089A (en) 1983-11-22 1985-06-18 Olin Corporation Three-step plasma treatment of copper foils to enhance their laminate adhesion
DE3413019A1 (en) * 1984-04-06 1985-10-17 Robert Bosch Gmbh, 7000 Stuttgart METHOD FOR APPLYING A THIN, TRANSPARENT LAYER TO THE SURFACE OF OPTICAL ELEMENTS
JPH02101166A (en) * 1988-10-07 1990-04-12 Furukawa Alum Co Ltd Corrosion-resistant metallic sheet
US4980196A (en) 1990-02-14 1990-12-25 E. I. Du Pont De Nemours And Company Method of coating steel substrate using low temperature plasma processes and priming
US5156919A (en) * 1990-04-03 1992-10-20 Segate Technology, Inc. Fluorocarbon coated magnesium alloy carriage and method of coating a magnesium alloy shaped part
CS488890A3 (en) * 1990-10-08 1992-04-15 Rektorat Masarykovy Univerzity Process for making protective layer, particularly on piezo-resistant manometers and apparatus for making the same
DE4216999C2 (en) * 1992-05-22 1996-03-14 Fraunhofer Ges Forschung Process for the surface coating of silver objects and protective layer produced by this process
US5618619A (en) * 1994-03-03 1997-04-08 Monsanto Company Highly abrasion-resistant, flexible coatings for soft substrates

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010039939A1 (en) 2010-08-30 2012-03-01 Aktiebolaget Skf Method of adhesive coating a metallic substrate
WO2012028448A1 (en) 2010-08-30 2012-03-08 Aktiebolaget Skf Process for applying a bonding layer to a metallic substrate
DE102010039939B4 (en) * 2010-08-30 2015-01-08 Aktiebolaget Skf A method of adhesive coating a metallic substrate, coating a metallic surface and using the coated substrate as a seal
DE102018212540A1 (en) * 2018-07-27 2020-01-30 Bayerische Motoren Werke Aktiengesellschaft Method for coating a motor vehicle raw component and motor vehicle raw component

Also Published As

Publication number Publication date
DE19748240A1 (en) 1999-05-06
DK1027169T3 (en) 2002-04-02
HUP0401917A2 (en) 2004-12-28
HUP0401917A3 (en) 2005-04-28
EP1027169A2 (en) 2000-08-16
WO1999022878A2 (en) 1999-05-14
NO20002204D0 (en) 2000-04-28
DE59802863D1 (en) 2002-02-28
AU1662699A (en) 1999-05-24
US20020014325A1 (en) 2002-02-07
CZ297047B6 (en) 2006-08-16
DE19748240C2 (en) 2001-05-23
ATE211660T1 (en) 2002-01-15
US6528170B2 (en) 2003-03-04
KR20010031646A (en) 2001-04-16
NO20002204L (en) 2000-06-26
US6242054B1 (en) 2001-06-05
WO1999022878A3 (en) 1999-07-15
JP4263353B2 (en) 2009-05-13
JP2001521820A (en) 2001-11-13
NO326804B1 (en) 2009-02-16
KR100377025B1 (en) 2003-03-26
CZ20001530A3 (en) 2001-12-12
ES2172252T3 (en) 2002-09-16

Similar Documents

Publication Publication Date Title
EP1027169B1 (en) Method for corrosion-resistant coating of metal substrates by means of plasma polymerisation
EP1870489B1 (en) Method to obtain a corrosion-resistant and shiny substrate
EP1432529B1 (en) Article having a plasmapolymer coating
EP2752504B1 (en) Method for producing a corrosion resistant, glossy, metallic coated substrate, the metallic coated substrate, and its use
EP2616191B1 (en) Method for coating surfaces and use of the articles coated using said method
EP1485622A1 (en) Method for coating objects
WO2007025868A1 (en) Coated articles
EP3219770A1 (en) Coating compositions comprising a polymer of 2,3,3,3-tetrafluoropropene and a film-forming polymer
EP0570944B1 (en) Process for coating silver objects and coating made by this process
Woo et al. Electrodeposition of organofunctional silanes and its influence on structural adhesive bonding
WO2007051806A1 (en) Coating method and coated body
WO2015044247A1 (en) Solid plasma polymer body (in particular plasma polymer layer)
DE19832299B4 (en) Process for improving the corrosion protection of rare earth magnets
DE2263038C3 (en) Process for coating aluminum or aluminum alloy material
DE10103460B4 (en) Multilayer plasma polymer coating, process for its preparation and its use
Grimmer Wetting, de-icing and anti-icing behavior of microstructured and plasma-coated polyurethane films
Lumjeak et al. Super hydrophobicity of sputtered PTFE films on nanotextured aluminum surface
DE69836908T2 (en) METAL CORROSION PROTECTION WITH WASHCOAT OF POLYPHENYLENE OXIDE
Reddy et al. The effect of interfacial tension on the adhesion of cathodic E-coat to aluminum alloys
DE102007046925A1 (en) Method for producing a metallic and/or non-metallic substrate, which is protected against corrosion in regions and/or is shiny, comprises provisioning a substrate or a carrier layer having a surface, which is coated in regions
Polat et al. Properties of Alumina Coating Formed by Microarc Oxidation Technique on 6061 Aluminum Alloy
DE102008037851A1 (en) Production of high-gloss/metal-coated layers on substrates for vehicle wheel, comprises pre-treating surface of the substrate, applying first base layer for surface smoothing, and applying second base layer for producing high gloss layer

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

17P Request for examination filed

Effective date: 20000503

AK Designated contracting states

Kind code of ref document: A2

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

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

RBV Designated contracting states (corrected)

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

17Q First examination report despatched

Effective date: 20010208

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

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

Owner name: FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DER ANGEWAN

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

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

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

AK Designated contracting states

Kind code of ref document: B1

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

REF Corresponds to:

Ref document number: 211660

Country of ref document: AT

Date of ref document: 20020115

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: PA ALDO ROEMPLER

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

REF Corresponds to:

Ref document number: 59802863

Country of ref document: DE

Date of ref document: 20020228

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20020406

ET Fr: translation filed
REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20020401106

Country of ref document: GR

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2172252

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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
REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DER ANGEWA

Free format text: FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DER ANGEWANDTEN FORSCHUNG E.V.#LEONRODSTRASSE 54#80636 MUENCHEN (DE) -TRANSFER TO- FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DER ANGEWANDTEN FORSCHUNG E.V.#HANSASTRASSE 27 C#80686 MUENCHEN (DE)

REG Reference to a national code

Ref country code: CH

Ref legal event code: PCAR

Free format text: ALDO ROEMPLER PATENTANWALT;BRENDENWEG 11 POSTFACH 154;9424 RHEINECK (CH)

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20121025

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IE

Payment date: 20121026

Year of fee payment: 15

Ref country code: BE

Payment date: 20121022

Year of fee payment: 15

Ref country code: FI

Payment date: 20121022

Year of fee payment: 15

Ref country code: FR

Payment date: 20121113

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20121023

Year of fee payment: 15

Ref country code: SE

Payment date: 20121024

Year of fee payment: 15

Ref country code: ES

Payment date: 20121023

Year of fee payment: 15

Ref country code: GR

Payment date: 20121029

Year of fee payment: 15

Ref country code: IT

Payment date: 20121024

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20121018

Year of fee payment: 15

BERE Be: lapsed

Owner name: *FRAUNHOFER-GESELLSCHAFT ZUR FORDERUNG DER ANGEWAN

Effective date: 20131031

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20140501

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

Effective date: 20131031

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20131029

REG Reference to a national code

Ref country code: GR

Ref legal event code: ML

Ref document number: 20020401106

Country of ref document: GR

Effective date: 20140505

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: GB

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

Effective date: 20131029

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20140630

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

Ref country code: GR

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

Effective date: 20140505

Ref country code: IT

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

Effective date: 20131029

Ref country code: FI

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

Effective date: 20131029

Ref country code: FR

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

Effective date: 20131031

Ref country code: SE

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

Effective date: 20131030

Ref country code: NL

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

Effective date: 20140501

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

Ref country code: BE

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

Effective date: 20131031

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

Ref country code: IE

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

Effective date: 20131029

Ref country code: DK

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

Effective date: 20131031

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20141107

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 NON-PAYMENT OF DUE FEES

Effective date: 20131030

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20171023

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20171023

Year of fee payment: 20

Ref country code: AT

Payment date: 20171018

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59802863

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK07

Ref document number: 211660

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181029