EP1027169A2 - Procede de revetement anticorrosion de substrats metalliques par polymerisation au plasma - Google Patents

Procede de revetement anticorrosion de substrats metalliques par polymerisation au plasma

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Publication number
EP1027169A2
EP1027169A2 EP98961076A EP98961076A EP1027169A2 EP 1027169 A2 EP1027169 A2 EP 1027169A2 EP 98961076 A EP98961076 A EP 98961076A EP 98961076 A EP98961076 A EP 98961076A EP 1027169 A2 EP1027169 A2 EP 1027169A2
Authority
EP
European Patent Office
Prior art keywords
plasma
corrosion
metal substrate
treatment
aluminum
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.)
Granted
Application number
EP98961076A
Other languages
German (de)
English (en)
Other versions
EP1027169B1 (fr
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 Foerderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Foerderung 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 Foerderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Publication of EP1027169A2 publication Critical patent/EP1027169A2/fr
Application granted granted Critical
Publication of EP1027169B1 publication Critical patent/EP1027169B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 ner driving for the corrosion-resistant coating of metal substrates by means of plasma polymerization.
  • Ner driving is particularly suitable for coating aluminum and aluminum alloys in a corrosion-resistant manner.
  • oxide layers in oxidizing plasmas are used as adhesion promoters, analogous to the usual painting processes, but also analogous to the surface preparation prior to bonding, which uses an oxide layer, usually generated by anodic oxidation.
  • the activation of the interface which is desirable for good adhesion, takes place, if at all, by Storage of alien substances.
  • the connection is made exclusively via adhesive forces.
  • coating or bonding systems have only moderate security against infiltration, since diffusion or water vapor formed by permeation processes weakens the connection between the material and the coating.
  • plasma polymerization is a process with which solid-state coatings with a predominantly organic character and excellent properties can be produced by the action of a plasma on an organic molecule in the gas phase.
  • Plasma polymerization belongs to the group of low-pressure plasma processes and is increasingly used industrially. The great interest in this technology can be attributed to the advantages of a fast, non-contact, dry chemical and little stressing coating process.
  • Plasma polymer layers deposited with low temperature plasmas are characterized as follows:
  • Plasma polymers are often three-dimensionally highly cross-linked, insoluble, hardly or not swelling and potentially good diffusion barriers.
  • 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, in particular up to approx. 60 ° C.
  • Finned tubes made of AlMgSi0.5 are widely used in condensing boilers. Such finned tubes do not always show sufficient corrosion resistance under extreme operating conditions and in limit areas with regard to the approved gas composition.
  • Paint systems are also not an alternative. Paints as surface protection lead to an impairment of heat conduction, which in the present case can only be tolerated within a narrow limit. Furthermore, with conventional lacquer coatings, water vapor diffusion leads to infiltration of the protective layer. During the subsequent condensation This causes the layer to lift off the metal surface and accelerate the corrosion process, as is known from localized types of corrosion.
  • a coating of such finned tubes for heat exchangers with a plasma polymer would be desirable in and of itself. Experiments in this regard, however, did not lead to corrosion-resistant coatings. As a rule, it was found that the plasma polymers did not adhere firmly enough to the metal surface and a more or less rapid infiltration of the coating took place, with the result that there were rapid signs of detachment.
  • a method for the surface coating of silver objects in which the surface is first treated with an ablating plasma and the surface is subsequently coated with a plasma polymer, firstly a coupling layer, then a permeation-preventing surface layer and finally one Sealing layer are generated.
  • ethylene and vinyltrimethylsilane are used for the coupling layer, ethylene for the permeation-preventing layer and hexamethyldisiloxane in combination with oxygen as plasma-forming monomers, with a continuous transition between the plasma-forming monomers taking place.
  • the coatings are largely scratch-resistant and form good tarnish protection, but can be set so that they can be removed with a cleaning agent.
  • a coating of aluminum substrates does not lead to corrosion-resistant coatings.
  • the plasma treatment again consists of two steps, firstly treating the surface with a reducing plasma that removes the surface, and secondly, in which the actual coating is applied directly to the plasma-pretreated metal layer.
  • the pretreatment, in particular smoothing of the surface of the metal substrate can be carried out using mechanical, chemical or electrochemical means. Combinations of mechanical and chemical smoothing are particularly preferred.
  • the mechanical and / or chemical smoothing can in any case be followed by electrochemical smoothing if the respective metal substrate allows this.
  • the electropolishing process is not suitable for surface treatment in finned tubes for physical / technical reasons. Here you have to rely on chemical processes such as acidic or alkaline pickling.
  • a combination of pickling in connection with a mechanical disturbance of the surface by wiping, brushing, blasting or the like can also be used come, in particular the workpiece with a liquid jet that contains the mordant and abrasive particles is applied.
  • the pickling process used to smooth the surface is a chemical process in which, with the help of aggressive chemicals, primarily oxide, rust and scale layers are removed from the respective metal surface.
  • Pickling liquids are mostly acids that attack both the cover layers and the metal itself.
  • Pickling is not a uniform process. Rather, different chemical and physical processes run side by side and also one after the other. The processes are often electrochemical in nature, with local elements being formed between the metal oxides and the metal surface.
  • Electropolishing is a process for shining metal surfaces in which elevations and burrs are removed electrolytically.
  • alkaline solutions can also be used for cleaning and pickling.
  • the surface is smoothed by the smoothing treatment down to an average roughness of less than 350 nm, preferably less than 250 nm.
  • an average center roughness of less than 100 nm can be achieved.
  • the smoothed surfaces obtained in this way are still not optimally suited for the application of a plasma polymer.
  • a plasma polymer is applied after mechanical / chemical and / or electrochemical smoothing, this does not yet show the desired service life under corrosive conditions.
  • the prerequisite for this is a further surface treatment using a reductively set plasma, in particular 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.
  • Further gases can be added to the hydrogen as the carrier of the plasma, for example hydrocarbons and in particular olefins, as described below, and also oxygen, nitrogen or argon, care being taken to maintain the reducing character.
  • the result of this plasma treatment is the achievement of an activated surface.
  • a reduction in the aluminum oxide layer and / or near-surface aluminum hydroxides on the metal surface is presumably brought about, so that Starting points for a reactive binding of a later applied plasma polymer directly to the metal.
  • Another side effect is that the surface is further smoothed by the plasma treatment.
  • a plasma polymer is deposited on the plasma-treated surface, preferably initially under further reducing conditions.
  • the main constituent of this plasma polymer is hydrocarbon and / or an organosilicon compound, which may contain oxygen, nitrogen or sulfur atoms, this hydrocarbon or organosilicon compound having a boiling point which is below the temperature and in the plasma coating chamber
  • alkanes, alkenes, aromatic hydrocarbons, silanes, siloxanes, silazanes and silathiane, preferably siloxanes are suitable for this.
  • the use of hexamethyldisiloxane and hexamethylcyclotrisiloxane is particularly preferred.
  • Other compounds are hexamethyldisilazane and hexamethylcyclotrisilazane, as well
  • Hexamethyldisilathian Hexamethyldisilathian. Higher homologues of these compounds and mixtures of such compounds can also be used, as can the partially or fully fluorinated derivatives.
  • Suitable co-monomers for the formation of the plasma polymer from organosilicon monomers are hydrocarbons, in particular olefins, for example ethylene, propene and cyclohexene.
  • Silanes, in particular vinyl-containing organosilicon compounds, can also be used as co-monomers, for example vinyltrimethylsilazane.
  • These unsaturated monomers can be admixed to the organosilicon compound containing O, N or S atoms in solid or changing proportions, a graded admixture being possible.
  • a transition layer can first be built up on the metal surface, which layer consists exclusively or predominantly of the organosilicon compound exists, and then the hydrocarbon is added.
  • the reverse procedure is also possible.
  • the properties of the plasma polymer coating can be changed such that there is optimal adhesion to the metal substrate and / or optimum resistance to corrosive substances.
  • Such a graded structure is known for example from DE-A-42 16 999.
  • plasma polymerization other gases can be fed in in addition to these monomers, for example oxygen, nitrogen or argon, in order to influence the properties of the plasma and the plasma polymer.
  • gases for example oxygen, nitrogen or argon, in order to influence the properties of the plasma and the plasma polymer.
  • the plasma polymerization generally takes place at a temperature of ⁇ 200 ° C., preferably ⁇ 100 ° C. and in particular about 60 ° C.
  • the pressure in the plasma coating chamber is generally ⁇ 10 mbar.
  • the layer formed by the plasma polymer formation on the metal substrate expediently has a thickness of 100 nm to 10 ⁇ m. However, it is readily possible to produce layer thicknesses of less than 100 nm for special purposes.
  • the surface is smoothed according to the invention by a leveling dressing, the effect of which is increased and evened out by a superimposed light mechanical component.
  • a leveling dressing the effect of which is increased and evened out by a superimposed light mechanical component.
  • an almost mirror-like, optically appealing surface is achieved on unstructured metal surfaces.
  • the thickness of the coating is no longer in the Surface structures of a rough metal surface "disappear", but an even, even layer is created.
  • a further increase in long-term corrosion resistance is achieved by installing a corrosion inhibitor which can be evaporated in vacuo, preferably in the lowest layer of the plasma polymer coating.
  • a corrosion inhibitor which can be evaporated in vacuo, preferably in the lowest layer of the plasma polymer coating.
  • it is not essential that such a corrosion inhibitor be applied directly to the substrate surface that is to say that it does not lie directly in the adhesion plane and thereby weaken it. Rather, a long-distance effect is achieved, which is particularly associated with the use of conductive polymers.
  • Suitable such polymers are, for example, polyanilines which have a low vapor pressure in vacuo or can be introduced into the plasma polymer in finely divided form in an amount of 0.1 to 1% by weight.
  • the technology described can also be applied to other metallic materials, in particular those which tend to form a surface oxide layer.
  • the method according to the invention can also be used to apply a plasma polymeric primer to a metal substrate, which is then subsequently supplemented by further coatings.
  • corrosion-resistant coatings can be achieved for a wide variety of purposes with a high coating thickness which has sufficient layer thickness for an abrasive stress.
  • Ormocere are particularly well suited for this.
  • the structure of Ormoceren coatings is similar to that of highly cross-linked plasma polymer coatings, but they can be built up in a vacuum without the relatively slow coating process become.
  • the typical layer thicknesses are of the order of 1 to 100 nm. The combination provides similarly good corrosion properties as with plasma polymer coatings alone.
  • the method according to the invention is particularly suitable for coating aluminum materials, the corrosion resistance achieved making the aluminum material particularly suitable for use as a heat exchanger and for producing finned tubes for heat exchangers in condensing boilers.
  • Rectangular samples made from AlMgSiO, 5 were used as test material.
  • the samples were first subjected to a multi-stage cleaning process to remove foreign substances such as oils and fats.
  • the surface of the sheets was then treated with a combined pickling and electropolishing process.
  • 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 butylene glycol was used as the electrolyte. Eletropolishing was carried out over a period of 180 s an electrolyte temperature of -15 to + 8 ° C, a polishing current of 5 to 18 A / dm and a polishing voltage of 19 to 11 V.
  • the sample was rinsed with water and in an ultrasonic bath for 10 min. treated in cold water. Finally, it was dried with hot air.
  • the workpiece Before the surface was smoothed, the workpiece had a matt surface with an average roughness of 0.570 ⁇ m (averaged from 5 measurements). After electropolishing, the center roughness was less than 100 nm. The surface was high-gloss.
  • the plasma treatment was carried out in a conventional plasma polymerization system, in which the monomer gas was introduced into the vacuum container and excited to form plasma by means of high-frequency alternating current and / or microwave energy.
  • the aluminum workpiece was exposed to a hydrogen plasma at 60 ° C and 50 mbar for 120 s.
  • the hydrogen was successively replaced by feeding hexamethyldisiloxane at a pressure of 10 mbar.
  • the volume flow was 500 ml / min.,
  • the output was max. 5 KW.
  • the application took place in a layer thickness of 500 nm.
  • the example was varied in such a way that in the plasma polymerization a plasma polymer of ethylene as a monomer was first applied to the metal surface, to which hexamethyldisiloxane was added in increasing amounts until the ethylene was completely displaced.
  • oxygen and nitrogen were added to the monomers as additional gases.
  • the plasma polymer layer has a good connection to the metal surface.
  • the plasma polymeric layer is amorphous and practically free of defects, i. H. it has no pores or inclusions.
  • the aluminum sheets coated according to the invention proved absolutely stable at 350 ° C. under conditions such as those prevailing in a heat exchanger for condensing boilers. They also have a reduced surface tension, which is why there is less tendency towards mineral deposits, for example in the form of scale. The reduced surface tension also protects against biological growth, for example on 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)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (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)
  • Coating By Spraying Or Casting (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

L'invention concerne un procédé de revêtement anticorrosion de substrats métalliques par polymérisation au plasma, caractérisé en ce que le substrat est soumis, dans une étape de prétraitement, à un lissage mécanique, chimique et/ou électrochimique, puis exposé à un plasma, à une température inférieure à 200 DEG C et à une pression de 10<-5> à 100 mbar, en ce qu'on active la surface, dans une première étape, dans un plasma réducteur et, dans une deuxième étape, on sépare le polymère d'un plasma renfermant au moins un composé hydrocarburé ou organo-silicique volatilisable dans les conditions du plasma, renfermant éventuellement de l'oxygène, de l'azote ou du soufre et pouvant contenir du fluor.
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 true EP1027169A2 (fr) 2000-08-16
EP1027169B1 EP1027169B1 (fr) 2002-01-09

Family

ID=7847280

Family Applications (1)

Application Number Title Priority Date Filing Date
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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NO326804B1 (no) 2009-02-16
DK1027169T3 (da) 2002-04-02
US6242054B1 (en) 2001-06-05
JP2001521820A (ja) 2001-11-13
NO20002204D0 (no) 2000-04-28
ES2172252T3 (es) 2002-09-16
DE59802863D1 (de) 2002-02-28
KR20010031646A (ko) 2001-04-16
NO20002204L (no) 2000-06-26
CZ297047B6 (cs) 2006-08-16
JP4263353B2 (ja) 2009-05-13
AU1662699A (en) 1999-05-24
EP1027169B1 (fr) 2002-01-09
WO1999022878A2 (fr) 1999-05-14
DE19748240A1 (de) 1999-05-06
HUP0401917A2 (hu) 2004-12-28
WO1999022878A3 (fr) 1999-07-15
CZ20001530A3 (cs) 2001-12-12
DE19748240C2 (de) 2001-05-23
ATE211660T1 (de) 2002-01-15
KR100377025B1 (ko) 2003-03-26
US20020014325A1 (en) 2002-02-07
US6528170B2 (en) 2003-03-04
HUP0401917A3 (en) 2005-04-28

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