EP1027169B1 - Procede de revetement anticorrosion de substrats metalliques par polymerisation au plasma - Google Patents

Procede de revetement anticorrosion de substrats metalliques par polymerisation au plasma Download PDF

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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
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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
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EP19980961076
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German (de)
English (en)
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EP1027169A2 (fr
Inventor
Wolfgang Semrau
Alfred Baalmann
Henning Stuke
Klaus-Dieter Vissing
Hartmut Hufenbach
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment 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
    • B05D3/14—Pretreatment 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
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of 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,

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physical Vapour Deposition (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)
  • Chemical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Formation Of Insulating Films (AREA)

Claims (19)

  1. Procédé de revêtement résistant à la corrosion de substrats métalliques au moyen d'une polymérisation à plasma,
    caractérisé en ce qu'
    on soumet le substrat, dans une étape de prétraitement, à un lissage mécanique, chimique et/ou électrochimique, puis on l'expose à une température inférieure à 200°C et à une pression de 10-5 à 100 mbar à un plasma, opération dans laquelle, dans une première étape, on active la surface dans un plasma réducteur, et dans une seconde étape, on dépose un polymère plasmatique constitué d'un plasma qui contient au moins un composé organique d'hydrocarbure ou de silicium, vaporisable dans les conditions du plasma, contenant au moins le cas échéant un atome d'oxygène, d'azote ou de soufre, ce composé pouvant contenir des atomes de fluor.
  2. Procédé selon la revendication 1,
    caractérisé en ce que
    le substrat métallique est l'aluminium ou un alliage d'aluminium.
  3. Procédé selon la revendication 1 ou 2,
    caractérisé en ce qu'
    on soumet le substrat métallique à une combinaison de traitement de surface métallique et de mordançage.
  4. Procédé selon l'une des revendications précédentes,
    caractérisé en ce qu'
    on polit électrochimiquement le substrat métallique.
  5. Procédé selon l'une des revendications précédentes,
    caractérisé par une rugosité moyenne du substrat métallique après traitement de lissage inférieure à 350 nm.
  6. Procédé selon l'une des revendications précédentes,
    caractérisé en ce que
    le traitement plasmatique s'effectue à une température inférieure ou égale à 100°C.
  7. Procédé selon l'une des revendications précédentes,
    caractérisé en ce que
    dans la première étape du traitement au plasma on active la surface avec un plasma à l'hydrogène à une pression ≤ 100 mbar.
  8. Procédé selon l'une des revendications précédentes,
    caractérisé en ce que
    le composé d'organosilicium dans la seconde étape du traitement au plasma contient un siloxane, un silazane ou un silathiane.
  9. Procédé selon la revendication 8,
    caractérisé en ce qu'
    on utilise un siloxane, en particulier l'hexaméthyl disiloxane ou l'hexaméthyl cyclotrisiloxane.
  10. Procédé selon l'une des revendications précédentes,
    caractérisé en ce que
    le plasma contient un hydrocarbure, en particulier une oléfine.
  11. Procédé selon la revendication 10,
    caractérisé en ce que
    l'hydrocarbure est l'éthylène, le propylène ou le cyclohexène.
  12. Procédé selon l'une des revendications précédentes,
    caractérisé en ce que
    le dépôt dans la seconde étape de traitement au plasma s'effectue à une pression ≤ 10 mbar et dans des conditions tout d'abord réductrices.
  13. Procédé selon l'une des revendications précédentes,
    caractérisé en ce qu'
    on introduit de l'oxygène, de l'azote et/ou un gaz rare dans le plasma.
  14. Procédé selon une des revendications précédentes,
    caractérisé en ce qu'on dépose la couche de polymère plasmatique en une épaisseur de 100 nm à 1 µm.
  15. Procédé selon l'une des revendications précédentes,
    caractérisé en ce qu'
    on introduit dans le polymère plasmatique un inhibiteur de corrosion.
  16. Procédé selon la revendication 15,
    caractérisé en ce qu'
    l'inhibiteur de corrosion est une polyaniline en une quantité de ,01 à 1 % en poids.
  17. Procédé selon l'une des revendications précédentes,
    caractérisé en ce qu'
    on munit d'une couche supplémentaire le substrat métallique revêtu de plasma.
  18. Application du procédé selon l'une des revendications précédentes à un échangeur d'ions en aluminium, en particulier sous forme de tubes à nervures.
  19. Substrat métallique présentant un revêtement anti-corrosion,
    caractérisé en ce qu'on l'obtient selon un procédé d'une des revendications 1 à 17.
EP19980961076 1997-10-31 1998-10-29 Procede de revetement anticorrosion de substrats metalliques par polymerisation au plasma Expired - Lifetime EP1027169B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19748240 1997-10-31
DE19748240A DE19748240C2 (de) 1997-10-31 1997-10-31 Verfahren zur korrosionsfesten Beschichtung von Metallsubstraten mittels Plasmapolymerisation und dessen Anwendung
PCT/DE1998/003266 WO1999022878A2 (fr) 1997-10-31 1998-10-29 Procede de revetement anticorrosion de substrats metalliques par polymerisation au plasma

Publications (2)

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

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EP19980961076 Expired - Lifetime EP1027169B1 (fr) 1997-10-31 1998-10-29 Procede de revetement anticorrosion de substrats metalliques par polymerisation au plasma

Country Status (13)

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

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DE19748240C2 (de) 2001-05-23
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HUP0401917A3 (en) 2005-04-28
ES2172252T3 (es) 2002-09-16
DE59802863D1 (de) 2002-02-28
US6528170B2 (en) 2003-03-04
NO20002204D0 (no) 2000-04-28
KR20010031646A (ko) 2001-04-16
WO1999022878A3 (fr) 1999-07-15
CZ297047B6 (cs) 2006-08-16
HUP0401917A2 (hu) 2004-12-28
CZ20001530A3 (cs) 2001-12-12
JP4263353B2 (ja) 2009-05-13
ATE211660T1 (de) 2002-01-15
KR100377025B1 (ko) 2003-03-26
DE19748240A1 (de) 1999-05-06
EP1027169A2 (fr) 2000-08-16
US20020014325A1 (en) 2002-02-07
US6242054B1 (en) 2001-06-05
NO20002204L (no) 2000-06-26
AU1662699A (en) 1999-05-24
DK1027169T3 (da) 2002-04-02
WO1999022878A2 (fr) 1999-05-14

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